Molecule having pesticidal utility, and compositions, and processes, related thereto

ABSTRACT

This disclosure relates to the field of molecules having pesticidal utility against pests in Phyla Arthropoda, Mollusca, and Nematoda, processes to produce such molecules, pesticidal compositions containing such molecules, and processes of using such pesticidal compositions against such pests. These pesticidal compositions may be used, for example, as acaricides, insecticides, miticides, molluscicides, and nematicides. This document discloses a molecule having the following formula.Formula One also known as F1

CROSS-REFERENCE TO RELATED APPLICATIONS

This Application is a continuation of, and claims the benefit of, U.S.nonprovisional application Ser. No. 16/416,382, which was filed May 20,2019, and which is now allowed; and claims the benefit of, and priorityfrom, U.S. provisional application Ser. No. 62/682,248; which was filedon Jun. 8, 2018. The entire contents of the above-identified applicationare hereby incorporated by reference into this Application.

FIELD OF THIS DISCLOSURE

This disclosure relates to the field of molecules having pesticidalutility against pests in Phyla Arthropoda, Mollusca, and Nematoda,processes to produce such molecules, pesticidal compositions containingsuch molecules, and processes of using such pesticidal compositionsagainst such pests. These pesticidal compositions may be used, forexample, as acaricides, insecticides, miticides, molluscicides, andnematicides.

BACKGROUND OF THIS DISCLOSURE

“Many of the most dangerous human diseases are transmitted by insectvectors” (Rivero et al.). “Historically, malaria, dengue, yellow fever,plague, filariasis, louse-borne typhus, trypanomiasis, leishmaniasis,and other vector borne diseases were responsible for more human diseaseand death in the 17^(th) through the early 20^(th) centuries than allother causes combined” (Gubler). Vector-borne diseases are responsiblefor about 17% of the global parasitic and infectious diseases. Malariaalone causes over 800,000 deaths a year, 85% of which occur in childrenunder five years of age. Each year there are about 50 to about 100million cases of dengue fever. A further 250,000 to 500,000 cases ofdengue hemorrhagic fever occur each year (Matthews). Vector controlplays a critical role in the prevention and control of infectiousdiseases. However, insecticide resistance, including resistance tomultiple insecticides, has arisen in all insect species that are majorvectors of human diseases (Rivero et al.). Recently, more than 550arthropod species have developed resistance to at least one pesticide(Whalon et al.). Furthermore, the cases of insect resistance continue toexceed by far the number of cases of herbicide and fungicide resistance(Sparks et al.).

Each year insects, plant pathogens, and weeds, destroy more than 40% ofall food production. This loss occurs despite the application ofpesticides and the use of a wide array of non-chemical controls, suchas, crop rotations, and biological controls. If just some of this foodcould be saved, it could be used to feed the more than three billionpeople in the world who are malnourished (Pimental).

Plant parasitic nematodes are among the most widespread pests, and arefrequently one of the most insidious and costly. It has been estimatedthat losses attributable to nematodes are from about 9% in developedcountries to about 15% in undeveloped countries. However, in the UnitedStates of America a survey of 35 States on various crops indicatednematode-derived losses of up to 25% (Nicol et al.).

It is noted that gastropods (slugs and snails) are pests of lesseconomic importance than other arthropods or nematodes, but in certainplaces, they may reduce yields substantially, severely affecting thequality of harvested products, as well as, transmitting human, animal,and plant diseases. While only a few dozen species of gastropods areserious regional pests, a handful of species are important pests on aworldwide scale. In particular, gastropods affect a wide variety ofagricultural and horticultural crops, such as, arable, pastoral, andfiber crops; vegetables; bush and tree fruits; herbs; and ornamentals(Speiser).

Termites cause damage to all types of private and public structures, aswell as to agricultural and forestry resources. In 2005, it wasestimated that termites cause over US$50 billion in damage worldwideeach year (Korb).

Consequently, for many reasons, including those mentioned above, thereis an on-going need for the costly (estimated to be about US$256 millionper pesticide in 2010), time-consuming (on average about 10 years perpesticide), and difficult, development of new pesticides (CropLifeAmerica).

Certain References Cited in this Disclosure

CropLife America, The Cost of New Agrochemical Product Discovery,Development & Registration, and Research & Development predictions forthe Future, 2010.

Drewes, M., Tietjen, K., Sparks, T. C., High-Throughput Screening inAgrochemical Research, Modern Methods in Crop Protection Research, PartI, Methods for the Design and Optimization of New Active Ingredients,Edited by Jeschke, P., Kramer, W., Schirmer, U., and Matthias W., p.1-20, 2012.

Gubler, D., Resurgent Vector-Borne Diseases as a Global Health Problem,Emerging Infectious Diseases, Vol. 4, No. 3, p. 442-450, 1998.

Korb, J., Termites, Current Biology, Vol. 17, No. 23, 2007.

Matthews, G., Integrated Vector Management: Controlling Vectors ofMalaria and Other Insect Vector Borne Diseases, Ch. 1, p. 1, 2011.

Nicol, J., Turner S., Coyne, L., den Nijs, L., Hocksland, L.,Tahna-Maafi, Z., Current Nematode Threats to World Agriculture, Genomicand Molecular Genetics of Plant—Nematode Interactions, p. 21-43, 2011.

Pimental, D., Pest Control in World Agriculture, AgriculturalSciences—Vol. II, 2009.

Rivero, A., Vezilier, J., Weill, M., Read, A., Gandon, S., InsectControl of Vector-Borne Diseases: When is Insect Resistance a Problem?Public Library of Science Pathogens, Vol. 6, No. 8, p. 1-9, 2010.

Sparks T. C., Nauen R., IRAC: Mode of action classification andinsecticide resistance management, Pesticide Biochemistry and Physiology(2014) available online 4 Dec. 2014.

Speiser, B., Molluscicides, Encyclopedia of Pest Management, Ch. 219, p.506-508, 2002.

Whalon, M., Mota-Sanchez, D., Hollingworth, R., Analysis of GlobalPesticide Resistance in Arthropods, Global Pesticide Resistance inArthropods, Ch. 1, p. 5-33, 2008.

Definitions Used in this Disclosure

The examples given in these definitions are generally non-exhaustive andmust not be construed as limiting this disclosure. It is understood thata substituent should comply with chemical bonding rules and stericcompatibility constraints in relation to the particular molecule towhich it is attached. These definitions are only to be used for thepurposes of this disclosure.

The phrase “active ingredient” means a material having activity usefulin controlling pests, and/or that is useful in helping other materialshave better activity in controlling pests, examples of such materialsinclude, but are not limited to, acaricides, algicides, antifeedants,avicides, bactericides, bird repellents, chemosterilants, fungicides,herbicide safeners, herbicides, insect attractants, insect repellents,insecticides, mammal repellents, mating disrupters, molluscicides,nematicides, plant activators, plant growth regulators, rodenticides,synergists, and virucides (see alanwood.net). Specific examples of suchmaterials include, but are not limited to, the materials listed inactive ingredient group alpha.

The phrase “active ingredient group alpha” (hereafter “AIGA”) meanscollectively the following materials:

(1) (3-ethoxypropyl)mercury bromide, 1,2-dibromoethane,1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropene, 1-MCP,1-methylcyclopropene, 1-naphthol, 2-(octylthio)ethanol, 2,3,3-TPA,2,3,5-tri-iodobenzoic acid, 2,3,6-TBA, 2,4,5-T, 2,4,5-TB, 2,4,5-TP,2,4-D, 2,4-DB, 2,4-DEB, 2,4-DEP, 2,4-DES, 2,4-DP, 2,4-MCPA, 2,4-MCPB,2iP, 2-methoxyethylmercury chloride, 2-phenylphenol, 3,4-DA, 3,4-DB,3,4-DP, 3,6-dichloropicolinic acid, 4-aminopyridine, 4-CPA, 4-CPB,4-CPP, 4-hydroxyphenethyl alcohol, 8-hydroxyquinoline sulfate,8-phenylmercurioxyquinoline, abamectin, abamectin-aminomethyl, abscisicacid, ACC, acephate, acequinocyl, acetamiprid, acethion, acetochlor,acetofenate, acetophos, acetoprole, acibenzolar, acifluorfen, aclonifen,ACN, acrep, acrinathrin, acrolein, acrylonitrile, acynonapyr, acypetacs,afidopyropen, afoxolaner, alachlor, alanap, alanycarb, albendazole,aldicarb, aldicarb sulfone, aldimorph, aldoxycarb, aldrin, allethrin,allicin, allidochlor, allosamidin, alloxydim, allyl alcohol, allyxycarb,alorac, a/pha-cypermethrin, a/pha-endosulfan, alphamethrin, altretamine,aluminium phosphide, aluminum phosphide, ametoctradin, ametridione,ametryn, ametryne, amibuzin, amicarbazone, amicarthiazol, amidithion,amidoflumet, amidosulfuron, aminocarb, aminocyclopyrachlor,aminopyralid, aminopyrifen, aminotriazole, amiprofos-methyl, amiprophos,amiprophos-methyl, amisulbrom, amiton, amitraz, amitrole, ammoniumsulfamate, amobam, amorphous silica gel, amorphous silicon dioxide,ampropylfos, AMS, anabasine, ancymidol, anilazine, anilofos, anisuron,anthraquinone, antu, apholate, aramite, arprocarb, arsenous oxide,asomate, aspirin, asulam, athidathion, atraton, atrazine, aureofungin,avermectin B1, AVG, aviglycine, azaconazole, azadirachtin, azafenidin,azamethiphos, azidithion, azimsulfuron, azinphosethyl, azinphos-ethyl,azinphosmethyl, azinphos-methyl, aziprotryn, aziprotryne, azithiram,azobenzene, azocyclotin, azothoate, azoxystrobin, bachmedesh, barban,barbanate, barium hexafluorosilicate, barium polysulfide, bariumsilicofluoride, barthrin, basic copper carbonate, basic copper chloride,basic copper sulfate, BCPC, beflubutamid, beflubutamid-M, benalaxyl,benalaxyl-M, benazolin, bencarbazone, benclothiaz, bendaqingbingzhi,bendiocarb, bendioxide, benefin, benfluralin, benfuracarb, benfuresate,benmihuangcaoan, benodanil, benomyl, benoxacor, benoxafos, benquinox,bensulfuron, bensulide, bensultap, bentaluron, bentazon, bentazone,benthiavalicarb, benthiazole, benthiocarb, bentranil, benzadox,benzalkonium chloride, benzamacril, benzamizole, benzamorf, benzenehexachloride, benzfendizone, benzimine, benzipram, benzobicyclon,benzoepin, benzofenap, benzofluor, benzohydroxamic acid, benzomate,benzophosphate, benzothiadiazole, benzovindiflupyr, benzoximate,benzoylprop, benzpyrimoxan, benzthiazuron, benzuocaotong, benzylbenzoate, benzyladenine, berberine, beta-cyfluthrin, beta-cypermethrin,bethoxazin, BHC, bialaphos, bicyclopyrone, bifenazate, bifenox,bifenthrin, bifujunzhi, bilanafos, binapacryl, bingqingxiao,bioallethrin, bioethanomethrin, biopermethrin, bioresmethrin, biphenyl,bisazir, bismerthiazol, bismerthiazol-copper, bisphenylmercurymethylenedi(x-naphthalene-y-sulphonate), bispyribac, bistrifluron,bisultap, bitertanol, bithionol, bixafen, bixlozone, blasticidin-S,borax, Bordeaux mixture, boric acid, boscalid, BPPS, brassinolide,brassinolide-ethyl, brevicomin, brodifacoum, brofenprox, brofenvalerate,broflanilide, brofluthrinate, bromacil, bromadiolone, bromchlophos,bromethalin, bromethrin, bromfenvinfos, bromoacetamide, bromobonil,bromobutide, bromociclen, bromocyclen, bromo-DDT, bromofenoxim,bromofos, bromomethane, bromophos, bromophos-ethyl, bromopropylate,bromothalonil, bromoxynil, brompyrazon, bromuconazole, bronopol, BRP,BTH, bucarpolate, bufencarb, buminafos, bupirimate, buprofezin, Burgundymixture, busulfan, busulphan, butacarb, butachlor, butafenacil, butam,butamifos, butane-fipronil, butathiofos, butenachlor, butene-fipronil,butethrin, buthidazole, buthiobate, buthiuron, butifos, butocarboxim,butonate, butopyronoxyl, butoxycarboxim, butralin, butrizol, butroxydim,buturon, butylamine, butylate, butylchlorophos, butylene-fipronil,cacodylic acid, cadusafos, cafenstrole, calciferol, calcium arsenate,calcium chlorate, calcium cyanamide, calcium cyanide, calciumpolysulfide, calvinphos, cambendichlor, camphechlor, camphor, captafol,captan, carbam, carbamorph, carbanolate, carbaril, carbaryl, carbasulam,carbathion, carbendazim, carbendazol, carbetamide, carbofenotion,carbofuran, carbon disulfide, carbon tetrachloride, carbonyl sulfide,carbophenothion, carbophos, carbosulfan, carboxazole, carboxide,carboxin, carfentrazone, carpropamid, cartap, carvacrol, carvone, CAVP,CDAA, CDEA, CDEC, cellocidin, CEPC, ceralure, cerenox, cevadilla,Cheshunt mixture, chinalphos, chinalphos-methyl, chinomethionat,chinomethionate, chiralaxyl, chitosan, chlobenthiazone, chlomethoxyfen,chloralose, chloramben, chloramine phosphorus, chloramphenicol,chloraniformethan, chloranil, chloranocryl, chlorantraniliprole,chlorazifop, chlorazine, chlorbenside, chlorbenzuron, chlorbicyclen,chlorbromuron, chlorbufam, chlordane, chlordecone, chlordimeform,chlorempenthrin, chloretazate, chlorethephon, chlorethoxyfos,chloreturon, chlorfenac, chlorfenapyr, chlorfenazole, chlorfenethol,chlorfenidim, chlorfenprop, chlorfenson, chlorfensulphide,chlorfenvinphos, chlorfenvinphos-methyl, chlorfluazuron, chlorflurazole,chlorflurecol, chlorfluren, chlorflurenol, chloridazon, chlorimuron,chlorinate, chlor-IPC, chlormephos, chlormequat, chlormesulone,chlormethoxynil, chlornidine, chlornitrofen, chloroacetic acid,chlorobenzilate, chlorodinitronaphthalenes, chlorofenizon, chloroform,chloromebuform, chloromethiuron, chloroneb, chlorophacinone, chlorophos,chloropicrin, chloropon, chloroprallethrin, chloropropylate,chlorothalonil, chlorotoluron, chloroxifenidim, chloroxuron,chloroxynil, chlorphonium, chlorphoxim, chlorprazophos, chlorprocarb,chlorpropham, chlorpyrifos, chlorpyrifos-methyl, chlorquinox,chlorsulfuron, chlorthal, chlorthiamid, chlorthiophos, chlortoluron,chlozolinate, chltosan, cholecalciferol, choline chloride,chromafenozide, cicloheximide, cimectacarb, cimetacarb, cinerin I,cinerin II, cinerins, cinidon-ethyl, cinmethylin, cinosulfuron,cintofen, ciobutide, cisanilide, cismethrin, clacyfos, clefoxydim,clenpirin, clenpyrin, clethodim, climbazole, cliodinate, clodinafop,cloethocarb, clofencet, clofenotane, clofentezine, clofenvinfos,clofibric acid, clofop, clomazone, clomeprop, clonitralid, cloprop,cloproxydim, clopyralid, cloquintocet, cloransulam, closantel,clothianidin, clotrimazole, cloxyfonac, cloxylacon, clozylacon, CMA,CMMP, CMP, CMU, codlelure, colecalciferol, colophonate, copper8-quinolinolate, copper acetate, copper acetoarsenite, copper arsenate,copper carbonate, basic, copper hydroxide, copper naphthenate, copperoleate, copper oxychloride, copper silicate, copper sulfate, coppersulfate, basic, copper zinc chromate, coumachlor, coumaféne, coumafos,coumafuryl, coumaphos, coumatetralyl, coumethoxystrobin, coumithoate,coumoxystrobin, CPMC, CPMF, CPPC, credazine, cresol, cresylic acid,crimidine, crotamiton, crotoxyfos, crotoxyphos, crufomate, cryolite,cue-lure, cufraneb, cumyleron, cumyluron, cuprobam, cuprous oxide,curcumenol, CVMP, cyanamide, cyanatryn, cyanazine, cyanofenphos,cyanogen, cyanophos, cyanthoate, cyantraniliprole, cyanuric acid,cyazofamid, cybutryne, cyclafuramid, cyclanilide, cyclaniliprole,cyclethrin, cycloate, cycloheximide, cycloprate, cycloprothrin,cyclopyranil, cyclopyrimorate, cyclosulfamuron, cycloxydim, cycluron,cyenopyrafen, cyflufenamid, cyflumetofen, cyfluthrin, cyhalodiamide,cyhalofop, cyhalothrin, cyhexatin, cymiazole, cymoxanil, cyometrinil,cypendazole, cypermethrin, cyperquat, cyphenothrin, cyprazine,cyprazole, cyproconazole, cyprodinil, cyprofuram, cypromid,cyprosulfamide, cyromazine, cythioate, cytrex, daimuron, dalapon,daminozide, dayoutong, dazomet, DBCP, d-camphor, DCB, DCIP, DCPA(Japan), DCPA (USA), DCPTA, DCU, DDD, DDPP, DDT, DDVP, debacarb,decafentin, decamethrin, decarbofuran, deet, dehydroacetic acid,deiquat, delachlor, delnav, deltamethrin, demephion, demephion-O,demephion-S, demeton, demeton-methyl, demeton-O, demeton-O-methyl,demeton-S, demeton-S-methyl, demeton-S-methyl sulphone,demeton-S-methylsulphon, DEP, depalléthrine, derris, desmedipham,desmetryn, desmetryne, d-fanshiluquebingjuzhi, diafenthiuron, dialifor,dialifos, diallate, di-allate, diamidafos, dianat, diatomaceous earth,diatomite, diazinon, dibrom, dibutyl phthalate, dibutyl succinate,dicamba, dicapthon, dichlobenil, dichlobentiazox, dichlofenthion,dichlofluanid, dichlone, dichloralurea, dichlorbenzuron, dichlorfenidim,dichlorflurecol, dichlorflurenol, dichlormate, dichlormid,dichloromethane, dichlorophen, dichlorprop, dichlorprop-P, dichlorvos,dichlozolin, dichlozoline, diclobutrazol, diclocymet, diclofop,diclomezine, dicloran, dicloromezotiaz, diclosulam, dicofol, dicophane,dicoumarol, dicresyl, dicrotophos, dicryl, dicumarol, dicyclanil,dicyclonon, dieldrin, dienochlor, diethamquat, diethatyl, diethion,diéthion, diethofencarb, dietholate, diéthon, diethyl pyrocarbonate,diethyltoluamide, difenacoum, difenoconazole, difenopenten, difenoxuron,difenzoquat, difethialone, diflovidazin, diflubenzuron, diflufenican,diflufenicanil, diflufenzopyr, diflumetorim, dikegulac, dilor, dimatif,dimefluthrin, dimefox, dimefuron, dimehypo, dimepiperate, dimetachlone,dimetan, dimethacarb, dimethachlone, dimethachlor, dimethametryn,dimethenamid, dimethenamid-P, dimethipin, dimethirimol, dimethoate,dimethomorph, dimethrin, dimethyl carbate, dimethyl disulfide, dimethylphthalate, dimethylvinphos, dimetilan, dimexano, dimidazon,dimoxystrobin, dimpropyridaz, dimpylate, dimuron, dinex, dingjunezuo,diniconazole, diniconazole-M, dinitramine, dinitrophenols, dinobuton,dinocap, dinocap-4, dinocap-6, dinocton, dinofenate, dinopenton,dinoprop, dinosam, dinoseb, dinosulfon, dinotefuran, dinoterb,dinoterbon, diofenolan, dioxabenzofos, dioxacarb, dioxathion, dioxation,diphacin, diphacinone, diphenadione, diphenamid, diphenamide, diphenylsulfone, diphenylamine, diphenylsulphide, diprogulic acid, dipropalin,dipropetryn, dipterex, dipymetitrone, dipyrithione, diquat, disodiumtetraborate, disosultap, disparlure, disugran, disul, disulfiram,disulfoton, ditalimfos, dithianon, dithicrofos, dithioether,dithiométon, dithiopyr, diuron, dixanthogen, d-limonene, DMDS, DMPA,DNOC, dodemorph, dodicin, dodine, dofenapyn, doguadine, dominicalure,doramectin, DPC, drazoxolon, DSMA, d-trans-allethrin,d-trans-resmethrin, dufulin, dymron, EBEP, EBP, ebufos, ecdysterone,echlomezol, EDB, EDC, EDDP, edifenphos, eglinazine, emamectin, EMPC,empenthrin, enadenine, endosulfan, endothal, endothall, endothion,endrin, enestroburin, enilconazole, enoxastrobin, ephirsulfonate, EPN,epocholeone, epofenonane, epoxiconazole, eprinomectin, epronaz,epsilon-metofluthrin, epsilon-momfluorothrin, EPTC, erbon,ergocalciferol, erlujixiancaoan, esdépalléthrine, esfenvalerate, ESP,esprocarb, etacelasil, etaconazole, etaphos, etem, ethaboxam, ethachlor,ethalfluralin, ethametsulfuron, ethaprochlor, ethephon, ethidimuron,ethiofencarb, ethiolate, ethion, ethiozin, ethiprole, ethirimol,ethoate-methyl, ethobenzanid, ethofumesate, ethohexadiol, ethoprop,ethoprophos, ethoxyfen, ethoxyquin, ethoxysulfuron, ethychlozate, ethylformate, ethyl pyrophosphate, ethylan, ethyl-DDD, ethylene, ethylenedibromide, ethylene dichloride, ethylene oxide, ethylicin, ethylmercury2,3-dihydroxypropyl mercaptide, ethylmercury acetate, ethylmercurybromide, ethylmercury chloride, ethylmercury phosphate, etinofen, ETM,etnipromid, etobenzanid, etofenprox, etoxazole, etridiazole, etrimfos,étrimphos, eugenol, EXD, famoxadone, famphur, fenac, fenamidone,fenaminosulf, fenaminstrobin, fenamiphos, fenapanil, fenarimol,fenasulam, fenazaflor, fenazaquin, fenbuconazole, fenbutatin oxide,fenchlorazole, fenchlorphos, fenclofos, fenclorim, fenethacarb,fenfluthrin, fenfuram, fenhexamid, fenidin, fenitropan, fenitrothion,fénizon, fenjuntong, fenobucarb, fenolovo, fenoprop, fenothiocarb,fenoxacrim, fenoxanil, fenoxaprop, fenoxaprop-P, fenoxasulfone,fenoxycarb, fenpiclonil, fenpicoxamid, fenpirithrin, fenpropathrin,fenpropidin, fenpropimorph, fenpyrazamine, fenpyroximate,fenquinotrione, fenridazon, fenson, fensulfothion, fenteracol,fenthiaprop, fenthion, fenthion-ethyl, fentiaprop, fentin, fentrazamide,fentrifanil, fenuron, fenuron-TCA, fenvalerate, ferbam, ferimzone,ferric phosphate, ferrous sulfate, fipronil, flamprop, flamprop-M,flazasulfuron, flocoumafen, flometoquin, flonicamid, florasulam,florpyrauxifen, florylpicoxamid, fluacrypyrim, fluazaindolizine,fluazifop, fluazifop-P, fluazinam, fluazolate, fluazuron, flubendiamide,flubenzimine, flubrocythrinate, flucarbazone, flucetosulfuron,fluchloralin, flucofuron, flucycloxuron, flucythrinate, fludioxonil,fluénéthyl, fluenetil, fluensulfone, flufenacet, flufenerim, flufenican,flufenoxuron, flufenoxystrobin, flufenprox, flufenpyr, flufenzine,flufiprole, fluhexafon, fluindapyr, flumethrin, flumetover, flumetralin,flumetsulam, flumezin, flumiclorac, flumioxazin, flumipropyn, flumorph,fluometuron, fluopicolide, fluopimomide, fluopyram, fluorbenside,fluoridamid, fluoroacetamide, fluoroacetic acid, fluorochloridone,fluorodifen, fluoroglycofen, fluoroimide, fluoromide, fluoromidine,fluoronitrofen, fluoroxypyr, fluothiuron, fluotrimazole, fluoxapiprolin,fluoxastrobin, flupoxam, flupropacil, flupropadine, flupropanate,flupyradifurone, flupyrimin, flupyrsulfuron, fluquinconazole,fluralaner, flurazole, flurecol, flurenol, fluridone, flurochloridone,fluromidine, fluroxypyr, flurprimidol, flursulamid, flurtamone,flusilazole, flusulfamide, flutenzine, fluthiacet, fluthiamide,flutianil, flutolanil, flutriafol, fluvalinate, fluxametamide,fluxapyroxad, fluxofenim, folpel, folpet, fomesafen, fonofos,foramsulfuron, forchlorfenuron, formaldehyde, formetanate, formothion,formparanate, fosamine, fosetyl, fosmethilan, fospirate, fosthiazate,fosthietan, frontalin, fthalide, fuberidazole, fucaojing, fucaomi,fujunmanzhi, fulumi, fumarin, funaihecaoling, fuphenthiourea, furalane,furalaxyl, furamethrin, furametpyr, furan tebufenozide, furathiocarb,furcarbanil, furconazole, furconazole-cis, furethrin, furfural,furilazole, furmecyclox, furophanate, furyloxyfen, gamma-BHC,gamma-cyhalothrin, gamma-HCH, genit, gibberellic acid, gibberellin A3,gibberellins, gliftor, glitor, glucochloralose, glufosinate,glufosinate-P, glyodin, glyoxime, glyphosate, glyphosine, gossyplure,grandlure, griseofulvin, guanoctine, guazatine, halacrinate, halauxifen,halfenprox, halofenozide, halosafen, halosulfuron, haloxydine,haloxyfop, haloxyfop-P, haloxyfop-R, HCA, HCB, HCH, hemel, hempa, HEOD,heptachlor, heptafluthrin, heptenophos, heptopargil, herbimycin,herbimycin A, heterophos, hexachlor, hexachloran, hexachloroacetone,hexachlorobenzene, hexachlorobutadiene, hexachlorophene, hexaconazole,hexaflumuron, hexafluoramin, hexaflurate, hexalure, hexamide,hexazinone, hexylthiofos, hexythiazox, HHDN, holosulf, homobrassinolide,huancaiwo, huanchongjing, huangcaoling, huanjunzuo, hydramethylnon,hydrargaphen, hydrated lime, hydrogen cyanamide, hydrogen cyanide,hydroprene, hydroxyisoxazole, hymexazol, hyquincarb, IAA, IBA, IBP,icaridin, imazalil, imazamethabenz, imazamox, imazapic, imazapyr,imazaquin, imazethapyr, imazosulfuron, imibenconazole, imicyafos,imidacloprid, imidaclothiz, iminoctadine, imiprothrin, inabenfide,indanofan, indaziflam, indoxacarb, inezin, infusorial earth,inpyrfluxam, iodobonil, iodocarb, iodofenphos, iodomethane,iodosulfuron, iofensulfuron, ioxynil, ipazine, IPC, ipconazole,ipfencarbazone, ipfentrifluconazole, ipflufenoquin, iprobenfos,iprodione, iprovalicarb, iprymidam, ipsdienol, ipsenol, IPSP, IPX,isamidofos, isazofos, isobenzan, isocarbamid, isocarbamide,isocarbophos, isocil, isocycloseram, isodrin, isofenphos,isofenphos-methyl, isofetamid, isoflucypram, isolan, isomethiozin,isonoruron, isopamphos, isopolinate, isoprocarb, isoprocil, isopropalin,isopropazol, isoprothiolane, isoproturon, isopyrazam, isopyrimol,isothioate, isotianil, isouron, isovaledione, isoxaben, isoxachlortole,isoxadifen, isoxaflutole, isoxapyrifop, isoxathion, isuron, ivermectin,ixoxaben, izopamfos, izopamphos, japonilure, japothrins, jasmolin I,jasmolin II, jasmonic acid, jiahuangchongzong, jiajizengxiaolin,jiaxiangjunzhi, jiecaowan, jiecaoxi, Jinganmycin A, jodfenphos, juvenilehormone I, juvenile hormone II, juvenile hormone III, kadethrin,kappa-bifenthrin, kappa-tefluthrin, karbutilate, karetazan, kasugamycin,kejunlin, kelevan, ketospiradox, kieselguhr, kinetin, kinoprene,kiralaxyl, kresoxim-methyl, kuicaoxi, lactofen, lambda-cyhalothrin,lancotrione, latilure, lead arsenate, lenacil, lepimectin, leptophos,lianbenjingzhi, lime sulfur, lindane, lineatin, linuron, lirimfos,litlure, looplure, lotilaner, lufenuron, lüfuqingchongxianan,lüxiancaolin, lvdingjunzhi, lvfumijvzhi, Ivxiancaolin, lythidathion,M-74, M-81, MAA, magnesium phosphide, malathion, maldison, maleichydrazide, malonoben, maltodextrin, MAMA, mancopper, mancozeb,mandestrobin, mandipropamid, maneb, matrine, mazidox, MCC, MCP, MCPA,MCPA-thioethyl, MCPB, MCPP, mebenil, mecarbam, mecarbinzid, mecarphon,mecoprop, mecoprop-P, medimeform, medinoterb, medlure, mefenacet,mefenoxam, mefenpyr, mefentrifluconazole, mefluidide, megatomoic acid,melissyl alcohol, melitoxin, MEMC, menazon, MEP, mepanipyrim,meperfluthrin, mephenate, mephosfolan, mepiquat, mepronil,meptyldinocap, mercaptodimethur, mercaptophos, mercaptophos thiol,mercaptothion, mercuric chloride, mercuric oxide, mercurous chloride,merphos, merphos oxide, mesoprazine, mesosulfuron, mesotrione, mesulfen,mesulfenfos, mesulphen, metacresol, metaflumizone, metalaxyl,metalaxyl-M, metaldehyde, metam, metamifop, metamitron, metaphos,metaxon, metazachlor, metazosulfuron, metazoxolon, metcamifen,metconazole, metepa, metflurazon, methabenzthiazuron, methacrifos,methalpropalin, metham, methamidophos, methasulfocarb, methazole,methfuroxam, methibenzuron, methidathion, methiobencarb, methiocarb,methiopyrisulfuron, methiotepa, methiozolin, methiuron, methocrotophos,métholcarb, methometon, methomyl, methoprene, methoprotryn,methoprotryne, methoquin-butyl, methothrin, methoxychlor,methoxyfenozide, methoxyphenone, methyl apholate, methyl bromide, methyleugenol, methyl iodide, methyl isothiocyanate, methyl parathion,methylacetophos, methylchloroform, methyldithiocarbamic acid,methyldymron, methylene chloride, methyl-isofenphos, methylmercaptophos,methylmercaptophos oxide, methylmercaptophos thiol, methylmercurybenzoate, methylmercury dicyandiamide, methylmercurypentachlorophenoxide, methylneodecanamide, methylnitrophos,methyltriazothion, metiozolin, metiram, metiram-zinc, metobenzuron,metobromuron, metofluthrin, metolachlor, metolcarb, metometuron,metominostrobin, metosulam, metoxadiazone, metoxuron, metrafenone,metriam, metribuzin, metrifonate, metriphonate, metsulfovax,metsulfuron, metyltetraprole, mevinphos, mexacarbate, miechuwei,mieshuan, miewenjuzhi, milbemectin, milbemycin oxime, milneb, mimanan,mipafox, MIPC, mirex, MNAF, moguchun, molinate, molosultap,momfluorothrin, monalide, monisuron, monoamitraz, monochloroacetic acid,monocrotophos, monolinuron, monomehypo, monosulfiram, monosulfuron,monosultap, monuron, monuron-TCA, morfamquat, moroxydine, morphothion,morzid, moxidectin, MPMC, MSMA, MTMC, muscalure, myclobutanil,myclozolin, myricyl alcohol, N-(ethylmercury)-p-toluenesulphonanilide,NAA, NAAm, nabam, naftalofos, naled, naphthalene, naphthaleneacetamide,naphthalic anhydride, naphthalophos, naphthoxyacetic acids,naphthylacetic acids, naphthylindane-1,3-diones, naphthyloxyaceticacids, naproanilide, napropamide, napropamide-M, naptalam, natamycin,NBPOS, neburea, neburon, nendrin, neonicotine, nichlorfos, niclofen,niclosamide, nicobifen, nicosulfuron, nicotine, nicotine sulfate,nifluridide, nikkomycins, NIP, nipyraclofen, nipyralofen, nitenpyram,nithiazine, nitralin, nitrapyrin, nitrilacarb, nitrofen, nitrofluorfen,nitrostyrene, nitrothal-isopropyl, nobormide, nonanol, norbormide,norea, norflurazon, nornicotine, noruron, novaluron, noviflumuron, NPA,nuarimol, nuranone, OCH, octachlorodipropyl ether, octhilinone,o-dichlorobenzene, ofurace, omethoate, o-phenylphenol, orbencarb,orfralure, orthobencarb, ortho-dichlorobenzene, orthosulfamuron,oryctalure, orysastrobin, oryzalin, osthol, osthole, ostramone, ovatron,ovex, oxabetrinil, oxadiargyl, oxadiazon, oxadixyl, oxamate, oxamyl,oxapyrazon, oxapyrazone, oxasulfuron, oxathiapiprolin, oxaziclomefone,oxazosulfyl, oxine-copper, oxine-Cu, oxolinic acid, oxpoconazole,oxycarboxin, oxydemeton-methyl, oxydeprofos, oxydisulfoton,oxyenadenine, oxyfluorfen, oxymatrine, oxytetracycline, oxythioquinox,PAC, paclobutrazol, paichongding, palléthrine, PAP,para-dichlorobenzene, parafluron, paraquat, parathion, parathion-methyl,parinol, Paris green, PCNB, PCP, PCP-Na, p-dichlorobenzene, PDJ,pebulate, pédinex, pefurazoate, pelargonic acid, penconazole,pencycuron, pendimethalin, penfenate, penflufen, penfluron, penoxalin,penoxsulam, pentachlorophenol, pentachlorophenyl laurate, pentanochlor,penthiopyrad, pentmethrin, pentoxazone, perchlordecone, perfluidone,permethrin, pethoxamid, PHC, phenamacril, phenamacril-ethyl,phénaminosulf, phenazine oxide, phénétacarbe, phenisopham, phenkapton,phenmedipham, phenmedipham-ethyl, phenobenzuron, phenothiol, phenothrin,phenproxide, phenthoate, phenylmercuriurea, phenylmercury acetate,phenylmercury chloride, phenylmercury derivative of pyrocatechol,phenylmercury nitrate, phenylmercury salicylate, phorate, phosacetim,phosalone, phosametine, phosazetim, phosazetin, phoscyclotin,phosdiphen, phosethyl, phosfolan, phosfolan-methyl, phosglycin, phosmet,phosnichlor, phosphamide, phosphamidon, phosphine, phosphinothricin,phosphocarb, phosphorus, phostin, phoxim, phoxim-methyl, phthalide,phthalophos, phthalthrin, picarbutrazox, picaridin, picloram,picolinafen, picoxystrobin, pimaricin, pindone, pinoxaden, piperalin,piperazine, piperonyl butoxide, piperonyl cyclonene, piperophos,piproctanly, piproctanyl, piprotal, pirimetaphos, pirimicarb, piriminil,pirimioxyphos, pirimiphos-ethyl, pirimiphos-methyl, pival, pivaldione,plifenate, PMA, PMP, polybutenes, polycarbamate, polychlorcamphene,polyethoxyquinoline, polyoxin D, polyoxins, polyoxorim, polythialan,potassium arsenite, potassium azide, potassium cyanate, potassiumethylxanthate, potassium naphthenate, potassium polysulfide, potassiumthiocyanate, pp′-DDT, prallethrin, precocene I, precocene II, precoceneIII, pretilachlor, primidophos, primisulfuron, probenazole, prochloraz,proclonol, procyazine, procymidone, prodiamine, profenofos, profluazol,profluralin, profluthrin, profoxydim, profurite-aminium, proglinazine,prohexadione, prohydrojasmon, promacyl, promecarb, prometon, prometryn,prometryne, promurit, pronamide, pronitridine, propachlor, propafos,propamidine, propamocarb, propanil, propaphos, propaquizafop,propargite, proparthrin, propazine, propetamphos, propham,propiconazole, propidine, propineb, propisochlor, propoxur,propoxycarbazone, propyl isome, propyrisulfuron, propyzamide,proquinazid, prosuler, prosulfalin, prosulfocarb, prosulfuron,prothidathion, prothiocarb, prothioconazole, prothiofos, prothoate,protrifenbute, proxan, prymidophos, prynachlor, psoralen, psoralene,pydanon, pydiflumetofen, pyflubumide, pymetrozine, pyracarbolid,pyraclofos, pyraclonil, pyraclostrobin, pyraflufen, pyrafluprole,pyramat, pyrametostrobin, pyraoxystrobin, pyrapropoyne, pyrasulfotole,pyraziflumid, pyrazolate, pyrazolynate, pyrazon, pyrazophos,pyrazosulfuron, pyrazothion, pyrazoxyfen, pyresmethrin, pyrethrin I,pyrethrin II, pyrethrins, pyribambenz-isopropyl, pyribambenz-propyl,pyribencarb, pyribenzoxim, pyributicarb, pyriclor, pyridaben,pyridachlometyl, pyridafol, pyridalyl, pyridaphenthion,pyridaphenthione, pyridate, pyridinitril, pyrifenox, pyrifluquinazon,pyriftalid, pyrimétaphos, pyrimethanil, pyrimicarbe, pyrimidifen,pyriminobac, pyriminostrobin, pyrimiphos-ethyl, pyrimiphos-methyl,pyrimisulfan, pyrimitate, pyrinuron, pyriofenone, pyriprole,pyripropanol, pyriproxyfen, pyrisoxazole, pyrithiobac, pyrolan,pyroquilon, pyroxasulfone, pyroxsulam, pyroxychlor, pyroxyfur,qincaosuan, qingkuling, quassia, quinacetol, quinalphos,quinalphos-methyl, quinazamid, quinclorac, quinconazole, quinmerac,quinoclamine, quinofumelin, quinomethionate, quinonamid, quinothion,quinoxyfen, quintiofos, quintozene, quizalofop, quizalofop-P, quwenzhi,quyingding, rabenzazole, rafoxanide, R-diniconazole, rebemide, reglone,renriduron, rescalure, resmethrin, rhodethanil, rhodojaponin-III,ribavirin, rimsulfuron, rizazole, R-metalaxyl, rodéthanil, ronnel,rotenone, ryania, sabadilla, saflufenacil, saijunmao, saisentong,salicylanilide, salifluofen, sanguinarine, santonin, S-bioallethrin,schradan, scilliroside, sebuthylazine, secbumeton, sedaxane, selamectin,semiamitraz, sesamex, sesamolin, sesone, sethoxydim, sevin,shuangjiaancaolin, shuangjianancaolin, S-hydroprene, siduron,sifumijvzhi, siglure, silafluofen, silatrane, silica aerogel, silicagel, silthiofam, silthiopham, silthiophan, silvex, simazine,simeconazole, simeton, simetryn, simetryne, sintofen, S-kinoprene,slaked lime, SMA, S-methoprene, S-metolachlor, sodium arsenite, sodiumazide, sodium chlorate, sodium cyanide, sodium fluoride, sodiumfluoroacetate, sodium hexafluorosilicate, sodium naphthenate, sodiumo-phenylphenoxide, sodium orthophenylphenoxide, sodiumpentachlorophenate, sodium pentachlorophenoxide, sodium polysulfide,sodium silicofluoride, sodium tetrathiocarbonate, sodium thiocyanate,solan, sophamide, spinetoram, spinosad, spirodiclofen, spiromesifen,spiropidion, spirotetramat, spiroxamine, stirofos, streptomycin,strychnine, sulcatol, sulcofuron, sulcotrione, sulfallate,sulfentrazone, sulfiram, sulfluramid, sulfodiazole, sulfometuron,sulfosate, sulfosulfuron, sulfotep, sulfotepp, sulfoxaflor, sulfoxide,sulfoxime, sulfur, sulfuric acid, sulfuryl fluoride, sulglycapin,sulphosate, sulprofos, sultropen, swep, tau-fluvalinate, tavron,tazimcarb, TBTO, TBZ, TCA, TCBA, TCMTB, TCNB, TDE, tebuconazole,tebufenozide, tebufenpyrad, tebufloquin, tebupirimfos, tebutam,tebuthiuron, tecloftalam, tecnazene, tecoram, tedion, teflubenzuron,tefluthrin, tefuryltrione, tembotrione, temefos, temephos, tepa, TEPP,tepraloxydim, teproloxydim, terallethrin, terbacil, terbucarb,terbuchlor, terbufos, terbumeton, terbuthylazine, terbutol, terbutryn,terbutryne, terraclor, terramicin, terramycin, tetcyclacis,tetflupyrolimet, tetrachlorantraniliprole, tetrachloroethane,tetrachlorvinphos, tetraconazole, tetradifon, tetradisul, tetrafluron,tetramethrin, tetramethylfluthrin, tetramine, tetranactin,tetraniliprole, tetrapion, tetrasul, thallium sulfate, thallous sulfate,thenylchlor, theta-cypermethrin, thiabendazole, thiacloprid,thiadiazine, thiadifluor, thiamethoxam, thiameturon, thiapronil,thiazafluron, thiazfluron, thiazone, thiazopyr, thicrofos, thicyofen,thidiazimin, thidiazuron, thiencarbazone, thifensulfuron, thifluzamide,thimerosal, thimet, thiobencarb, thiocarboxime, thiochlorfenphim,thiochlorphenphime, thiocyanatodinitrobenzenes, thiocyclam, thiodan,thiodiazole-copper, thiodicarb, thiofanocarb, thiofanox, thiofluoximate,thiohempa, thiomersal, thiometon, thionazin, thiophanate,thiophanate-ethyl, thiophanate-methyl, thiophos, thioquinox,thiosemicarbazide, thiosultap, thiotepa, thioxamyl, thiram, thiuram,thuringiensin, tiabendazole, tiadinil, tiafenacil, tiaojiean, TIBA,tifatol, tiocarbazil, tioclorim, tioxazafen, tioxymid, tirpate, TMTD,tolclofos-methyl, tolfenpyrad, tolprocarb, tolpyralate, tolyfluanid,tolylfluanid, tolylmercury acetate, tomarin, topramezone, toxaphene,TPN, tralkoxydim, tralocythrin, tralomethrin, tralopyril, transfluthrin,transpermethrin, tretamine, triacontanol, triadimefon, triadimenol,triafamone, triallate, tri-allate, triamiphos, triapenthenol,triarathene, triarimol, triasulfuron, triazamate, triazbutil,triaziflam, triazophos, triazothion, triazoxide, tribasic copperchloride, tribasic copper sulfate, tribenuron, tribufos, tributyltinoxide, tricamba, trichlamide, trichlopyr, trichlorfon,trichlormetaphos-3, trichloronat, trichloronate,trichlorotrinitrobenzenes, trichlorphon, triclopyr, triclopyricarb,tricresol, tricyclazole, tricyclohexyltin hydroxide, tridemorph,tridiphane, trietazine, trifenmorph, trifenofos, trifloxystrobin,trifloxysulfuron, trifludimoxazin, triflumezopyrim, triflumizole,triflumuron, trifluralin, triflusulfuron, trifop, trifopsime, triforine,trihydroxytriazine, trimedlure, trimethacarb, trimeturon, trinexapac,triphenyltin, triprene, tripropindan, triptolide, tritac, trithialan,triticonazole, tritosulfuron, trunc-call, tuoyelin, tyclopyrazoflor,uniconazole, uniconazole-P, urbacide, uredepa, valerate, validamycin,validamycin A, valifenalate, valone, vamidothion, vangard, vaniliprole,vernolate, vinclozolin, vitamin D3, warfarin, xiaochongliulin, xinjunan,xiwojunan, xiwojunzhi, XMC, xylachlor, xylenols, xylylcarb, xymiazole,yishijing, zarilamid, zeatin, zengxiaoan, zengxiaolin,zeta-cypermethrin, zinc naphthenate, zinc phosphide, zinc thiazole, zincthiozole, zinc trichlorophenate, zinc trichlorophenoxide, zineb, ziram,zolaprofos, zoocoumarin, zoxamide, zuoanjunzhi, zuocaoan, zuojunzhi,zuomihuanglong, α-chlorohydrin, α-ecdysone, α-multistriatin,α-naphthaleneacetic acids, and β-ecdysone;

-   -   (2) the following molecules in Table 1

TABLE 1 Structure of M# - active ingredients M# Structure M1

M2

M3

M4

As used in this disclosure, each of the above is an active ingredient.For more information consult the materials listed in the “Compendium ofPesticide Common Names,” located at Alanwood.net, and various editions,including the on-line edition, of “The Pesticide Manual” located atbcpcdata.com.

A particularly preferred selection of active ingredients are1,3-dichloropropene, chlorantraniliprole, chlorpyrifos,cyantraniliprole, hexaflumuron, methomyl, methoxyfenozide, noviflumuron,oxamyl, spinetoram, spinosad, sulfoxaflor, and triflumezopyrim(hereafter “AIGA-2”).

Additionally, another particularly preferred selection of activeingredients are acequinocyl, acetamiprid, acetoprole, avermectin,azinphos-methyl, bifenazate, bifenthrin, carbaryl, carbofuran,chlorfenapyr, chlorfluazuron, chromafenozide, clothianidin, cyfluthrin,cypermethrin, deltamethrin, diafenthiuron, emamectin benzoate,endosulfan, esfenvalerate, ethiprole, etoxazole, fipronil, flonicamid,fluacrypyrim, gamma-cyhalothrin, halofenozide, indoxacarb,lambda-cyhalothrin, lufenuron, malathion, methomyl, novaluron,permethrin, pyridalyl, pyrimidifen, spirodiclofen, tebufenozide,thiacloprid, thiamethoxam, thiodicarb, tolfenpyrad, andzeta-cypermethrin (hereafter “AIGA-3”).

The term “biopesticide” means a microbial biological pest control agentthat, in general, is applied in a similar manner to chemical pesticides.Commonly they are bacterial, but there are also examples of fungalcontrol agents, including Trichoderma spp. and Ampelomyces quisqualis.One well-known biopesticide example is Bacillus species, a bacterialdisease of Lepidoptera, Coleoptera, and Diptera. Biopesticides includeproducts based on entomopathogenic fungi (e.g. Metarhizium anisopliae),entomopathogenic nematodes (e.g. Steinernema feltiae), andentomopathogenic viruses (e.g. Cydia pomonella granulovirus). Otherexamples of entomopathogenic organisms include, but are not limited to,baculoviruses, protozoa, and Microsporidia. For the avoidance of doubt,biopesticides are active ingredients.

The term “locus” means a habitat, breeding ground, plant, seed, soil,material, or environment, in which a pest is growing, may grow, or maytraverse. For example, a locus may be: where crops, trees, fruits,cereals, fodder species, vines, turf, and/or ornamental plants, aregrowing; where domesticated animals are residing; the interior orexterior surfaces of buildings (such as places where grains are stored);the materials of construction used in buildings (such as impregnatedwood); and the soil around buildings.

The phrase “MoA Material” means an active ingredient having a mode ofaction (“MoA”) as indicated in IRAC MoA Classification v. 8.3, locatedat irac-online.org., which describes the following groups.

(1) Acetylcholinesterase (AChE) inhibitors, includes the followingactive ingredients Alanycarb, Aldicarb, Bendiocarb, Benfuracarb,Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan,Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb,Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur,Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC, Xylylcarb,Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Cadusafos,Chlorethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos,Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinon,Dichlorvos/DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Disulfoton,EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion,Fosthiazate, Heptenophos, Isofenphos, Isoxathion, Malathion, Mecarbam,Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate,Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phosalone,Phorate, Phosmet, Phosphamidon, Phoxim, Profenofos, Propetamphos,Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep,Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon,Triazophos, Trichlorfon, Vamidothion, Pirimiphos-methyl, Imicyafos, andIsopropyl O-(methoxyaminothio-phosphoryl) salicylate.

(2) GABA-gated chloride channel antagonists, includes the followingactive ingredients Chlordane, Endosulfan, Ethiprole, and Fipronil.

(3) Sodium channel modulators, includes the following active ingredientsAcrinathrin, Allethrin, d-cis-trans Allethrin, d-trans Allethrin,Bifenthrin, Bioallethrin, Bioallethrin S-cyclopentenyl, Bioresmethrin,Cycloprothrin, Cyfluthrin, beta-Cyfluthrin, Cyhalothrin,lambda-Cyhalothrin, gamma-Cyhalothrin, Cypermethrin, alpha-Cypermethrin,beta-Cypermethrin, theta-Cypermethrin, zeta-Cypermethrin, Cyphenothrin[(1R)-trans-isomers], Deltamethrin, Empenthrin [(EZ)-(1R)-isomers],Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate,Flumethrin, tau-Fluvalinate, Kadethrin, Pyrethrins (pyrethrum),Halfenprox, Phenothrin [(1R)-trans-isomer], Prallethrin, Resmethrin,Silafluofen, Tefluthrin, Tetramethrin, Tetramethrin [(1R)-isomers],Tralomethrin, Transfluthrin, Permethrin, DDT, and Methoxychlor.

(4) Nicotinic acetylcholine receptor (nAChR) agonists, includes thefollowing active ingredients

-   -   (4A) Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid,        Nitenpyram, Thiacloprid, Thiamethoxam    -   (4B) Nicotine,    -   (4C) Sulfoxaflor,    -   (4D) Flupyradifurone, and    -   (4E) Triflumezopyrim.

(5) Nicotinic acetylcholine receptor (nAChR) allosteric activators,includes the following active ingredients Spinetoram and Spinosad.

(6) Chloride channel activators, includes the following activeingredients Abamectin, Emamectin benzoate, Lepimectin, and Milbemectin.

(7) Juvenile hormone mimics, includes the following active ingredientsHydroprene, Kinoprene, Methoprene, Fenoxycarb, and Pyriproxyfen.

(8) Miscellaneous nonspecific (multi-site) inhibitors, includes thefollowing active ingredients Methyl Bromide, Chloropicrin, Cryolite,Sulfuryl fluoride, Borax, Boric acid, Disodium octaborate, Sodiumborate, Sodium metaborate, Tartar emetic, Diazomet, and Metam.

(9) Chordotonal organ TRPV channel modulators, includes the followingactive ingredients Afidopyropen, Pymetrozine and Pyrifluquinazon.

(10) Mite growth inhibitors, includes the following active ingredientsClofentezine, Hexythiazox, Diflovidazin, and Etoxazole.

(11) Microbial disruptors of insect midgut membranes, includes thefollowing active ingredients B.t. var. israelensis, B.t. var. aizawai,B.t. var. kurstaki, B.t. var. tenebrionenis, and Bacillus sphaericus.

(12) Inhibitors of mitochondrial ATP synthase, includes the followingactive ingredients Tetradifon, Propargite, Azocyclotin, Cyhexatin,Fenbutatin oxide, and Diafenthiuron.

(13) Uncouplers of oxidative phosphorylation via disruption of theproton gradient, includes the following active ingredients Chlorfenapyr,DNOC, and Sulfluramid.

(14) Nicotinic acetylcholine receptor (nAChR) channel blockers, includesthe following active ingredients Bensultap, Cartap hydrochloride,Thiocyclam, and Thiosultap-sodium.

(15) Inhibitors of chitin biosynthesis, type 0, includes the followingactive ingredients Bistrifluron, Chlorfluazuron, Diflubenzuron,Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron,Noviflumuron, Teflubenzuron, and Triflumuron.

(16) Inhibitors of chitin biosynthesis, type 1, includes the followingactive ingredient Buprofezin.

(17) Moulting disruptor, Dipteran, includes the following activeingredient Cyromazine.

(18) Ecdysone receptor agonists, includes the following activeingredients Chromafenozide, Halofenozide, Methoxyfenozide, andTebufenozide.

(19) Octopamine receptor agonists, includes the following activeingredient Amitraz.

(20) Mitochondrial complex III electron transport inhibitors, includesthe following active ingredients Hydramethylnon, Acequinocyl, Bifenazateand Fluacrypyrim.

(21) Mitochondrial complex I electron transport inhibitors, includes thefollowing active ingredients Fenazaquin, Fenpyroximate, Pyrimidifen,Pyridaben, Tebufenpyrad, Tolfenpyrad, and Rotenone.

(22) Voltage-dependent sodium channel blockers, includes the followingactive ingredients Indoxacarb and Metaflumizone.

(23) Inhibitors of acetyl CoA carboxylase, includes the following activeingredients Spirodiclofen, Spiromesifen, and Spirotetramat.

(24) Mitochondrial complex IV electron transport inhibitors, includesthe following active ingredients, Aluminium phosphide, Calciumphosphide, Phosphine, Zinc phosphide, and Cyanide.

(25) Mitochondrial complex II electron transport inhibitors, includesthe following active ingredients Cyenopyrafen, Cyflumetofen, andPyflubumide.

(28) Ryanodine receptor modulators, includes the following activeingredients Chlorantraniliprole, Cyantraniliprole, and Flubendiamide.

(29) Chordotonal Organ Modulators-undefined target site, includes thefollowing active ingredient Flonicamid.

Groups 26 and 27 are unassigned in this version of the classificationscheme. Additionally, there is a Group UN that contains activeingredients of unknown or uncertain mode of action. This group includesthe following active ingredients, Azadirachtin, Benzoximate,Bromopropylate, Chinomethionat, Dicofol, GS-omega/kappa HXTX-Hv1apeptide, Lime Sulfur, Pyridalyl, and Sulfur.

The term “pest” means an organism that is detrimental to humans, orhuman concerns (such as, crops, food, livestock, etc.), where saidorganism is from Phyla Arthropoda, Mollusca, or Nematoda. Particularexamples are ants, aphids, bed bugs, beetles, bristletails,caterpillars, cockroaches, crickets, earwigs, fleas, flies,grasshoppers, grubs, hornets, jassids, leafhoppers, lice, locusts,maggots, mealybugs, mites, moths, nematodes, plantbugs, planthoppers,psyllids, sawflies, scales, silverfish, slugs, snails, spiders,springtails, stink bugs, symphylans, termites, thrips, ticks, wasps,whiteflies, and wireworms.

Additional examples are pests in

(1) Subphyla Chelicerata, Myriapoda, and Hexapoda.

(2) Classes of Arachnida, Symphyla, and Insecta.

(3) Order Anoplura. A non-exhaustive list of particular genera includes,but is not limited to, Haematopinus spp., Hoplopleura spp., Linognathusspp., Pediculus spp., Polyplax spp., Solenopotes spp., andNeohaematopinis spp. A non-exhaustive list of particular speciesincludes, but is not limited to, Haematopinus asini, Haematopinus suis,Linognathus setosus, Linognathus ovillus, Pediculus humanus capitis,Pediculus humanus humanus, and Pthirus pubis.

(4) Order Coleoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Acanthoscelides spp., Agriotes spp.,Anthonomus spp., Apion spp., Apogonia spp., Araecerus spp., Aulacophoraspp., Bruchus spp., Cerosterna spp., Cerotoma spp., Ceutorhynchus spp.,Chaetocnema spp., Colaspis spp., Ctenicera spp., Curculio spp.,Cyclocephala spp., Diabrotica spp., Dinoderus spp., Gnathocerus spp.,Hemicoelus spp., Heterobostruchus spp., Hypera spp., Ips spp., Lyctusspp., Megascelis spp., Meligethes spp., Mezium spp., Niptus spp.,Otiorhynchus spp., Pantomorus spp., Phyllophaga spp., Phyllotreta spp.,Ptinus spp., Rhizotrogus spp., Rhynchites spp., Rhynchophorus spp.,Scolytus spp., Sphenophorus spp., Sitophilus spp., Tenebrio spp., andTribolium spp. A non-exhaustive list of particular species includes, butis not limited to, Acanthoscelides obtectus, Agrilus planipennis,Ahasverus advena, Alphitobius diaperinus, Anoplophora glabripennis,Anthonomus grandis, Anthrenus verbasci, Anthrenus falvipes, Ataeniusspretulus, Atomaria linearis, Attagenus unicolor, Bothynoderespunctiventris, Bruchus pisorum, Callosobruchus maculatus, Carpophilushemipterus, Cassida vittata, Cathartus quadricollis, Cerotomatrifurcata, Ceutorhynchus assimilis, Ceutorhynchus napi, Conoderusscalaris, Conoderus stigmosus, Conotrachelus nenuphar, Cotinis nitida,Crioceris asparagi, Cryptolestes ferrugineus, Cryptolestes pusillus,Cryptolestes turcicus, Cylindrocopturus adspersus, Deporaus marginatus,Dermestes lardarius, Dermestes maculatus, Epilachna varivestis,Euvrilletta peltata, Faustinus cubae, Hylobius pales, Hylotrupesbajulus, Hypera postica, Hypothenemus hampei, Lasioderma serricorne,Leptinotarsa decemlineata, Limonius canus, Liogenys fuscus, Liogenyssuturalis, Lissorhoptrus oryzophilus, Lophocateres pusillus, Lyctusplanicollis, Maecolaspis joliveti, Melanotus communis, Meligethesaeneus, Melolontha melolontha, Necrobia rufipes, Oberea brevis, Oberealinearis, Oryctes rhinoceros, Oryzaephilus mercator, Oryzaephilussurinamensis, Oulema melanopus, Oulema oryzae, Phyllophaga cuyabana,Polycaon stoutti, Popillia japonica, Prostephanus truncatus, Rhyzoperthadominica, Sitona lineatus, Sitophilus granarius, Sitophilus oryzae,Sitophilus zeamais, Stegobium paniceum, Tenebroides mauritanicus,Tribolium castaneum, Tribolium confusum, Trogoderma granarium,Trogoderma variabile, Xestobium rufovillosum, and Zabrus tenebrioides.

(5) Order Dermaptera. A non-exhaustive list of particular speciesincludes, but is not limited to, Fofficula auricularia.

(6) Order Blattaria. A non-exhaustive list of particular speciesincludes, but is not limited to, Blattella germanica, Blattellaasahinai, Blatta orientalis, Blatta lateralis, Parcoblattapennsylvanica, Periplaneta americana, Periplaneta australasiae,Periplaneta brunnea, Periplaneta fuliginosa, Pycnoscelus surinamensis,and Supella longipalpa.

(7) Order Diptera. A non-exhaustive list of particular genera includes,but is not limited to, Aedes spp., Agromyza spp., Anastrepha spp.,Anopheles spp., Bactrocera spp., Ceratitis spp., Chrysops spp.,Cochliomyia spp., Contarinia spp., Culex spp., Culicoides spp.,Dasineura spp., Delia spp., Drosophila spp., Fannia spp., Hylemya spp.,Liriomyza spp., Musca spp., Phorbia spp., Pollenia spp., Psychoda spp.,Simulium spp., Tabanus spp., and Tipula spp. A non-exhaustive list ofparticular species includes, but is not limited to, Agromyza frontella,Anastrepha suspensa, Anastrepha ludens, Anastrepha obliqua, Bactroceracucurbitae, Bactrocera dorsalis, Bactrocera invadens, Bactrocera zonata,Ceratitis capitata, Dasineura brassicae, Delia platura, Fanniacanicularis, Fannia scalaris, Gasterophilus intestinalis, Gracilliaperseae, Haematobia irritans, Hypoderma lineatum, Liriomyza brassicae,Liriomyza sativa, Melophagus ovinus, Musca autumnalis, Musca domestica,Oestrus ovis, Oscinella frit, Pegomya betae, Piophila casei, Psilarosae, Rhagoletis cerasi, Rhagoletis pomonella, Rhagoletis mendax,Sitodiplosis mosellana, and Stomoxys calcitrans.

(8) Order Hemiptera. A non-exhaustive list of particular generaincludes, but is not limited to, Adelges spp., Aulacaspis spp.,Aphrophora spp., Aphis spp., Bemisia spp., Ceroplastes spp., Chionaspisspp., Chrysomphalus spp., Coccus spp., Empoasca spp., Euschistus spp.,Lepidosaphes spp., Lagynotomus spp., Lygus spp., Macrosiphum spp.,Nephotettix spp., Nezara spp., Nilaparvata spp., Philaenus spp.,Phytocoris spp., Piezodorus spp., Planococcus spp., Pseudococcus spp.,Rhopalosiphum spp., Saissetia spp., Therioaphis spp., Toumeyella spp.,Toxoptera spp., Trialeurodes spp., Triatoma spp., and Unaspis spp. Anon-exhaustive list of particular species includes, but is not limitedto, Acrosternum hilare, Acyrthosiphon pisum, Aleyrodes proletella,Aleurodicus dispersus, Aleurothrixus floccosus, Amrasca biguttulabiguttula, Aonidiella aurantii, Aphis fabae, Aphis gossypii, Aphisglycines, Aphis pomi, Aulacorthum solani, Bactericera cockerelli,Bagrada hilaris, Bemisia argentifolii, Bemisia tabaci, Blissusleucopterus, Boisea trivittata, Brachycorynella asparagi, Brevenniarehi, Brevicoryne brassicae, Cacopsylla pyri, Cacopsylla pyricola,Calocoris norvegicus, Ceroplastes rubens, Cimex hemipterus, Cimexlectularius, Coccus pseudomagnoliarum, Dagbertus fasciatus, Dichelopsfurcatus, Diuraphis noxia, Diaphorina citri, Dysaphis plantaginea,Dysdercus suturellus, Edessa meditabunda, Empoasca vitis, Eriosomalanigerum, Erythroneura elegantula, Eurygaster maura, Euschistusconspersus, Euschistus heros, Euschistus servus, Halyomorpha halys,Helopeltis antonii, Hyalopterus pruni, Helopeltis antonii, Helopeltistheivora, Icerya purchasi, Idioscopus nitidulus, Jacobiasca formosana,Laodelphax striatellus, Lecanium corni, Leptocorisa oratorius,Leptocorisa varicornis, Lygus hesperus, Maconellicoccus hirsutus,Macrosiphum euphorbiae, Macrosiphum granarium, Macrosiphum rosae,Macrosteles quadrilineatus, Mahanarva frimbiolata, Megacopta cribraria,Metopolophium dirhodum, Mictis longicomis, Myzus persicae, Nasonoviaribisnigri, Nephotettix cincticeps, Neurocolpus longirostris, Nezaraviridula, Nilaparvata lugens, Paracoccus marginatus, Paratriozacockerelli, Parlatoria pergandii, Parlatoria ziziphi, Peregrinus maidis,Phylloxera vitifoliae, Physokermes piceae, Phytocoris califomicus,Phytocoris relativus, Piezodorus guildinii, Planococcus citri,Planococcus ficus, Poecilocapsus lineatus, Psallus vaccinicola,Pseudacysta perseae, Pseudococcus brevipes, Quadraspidiotus perniciosus,Rhopalosiphum maidis, Rhopalosiphum padi, Saissetia oleae, Scaptocoriscastanea, Schizaphis graminum, Sitobion avenae, Sogatella furcifera,Trialeurodes vaporariorum, Trialeurodes abutiloneus, Unaspis yanonensis,and Zulia entrerriana.

(9) Order Hymenoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Acromyrmex spp., Atta spp., Camponotusspp., Diprion spp., Dolichovespula spp., Formica spp., Monomorium spp.,Neodiprion spp., Paratrechina spp., Pheidole spp., Pogonomyrmex spp.,Polistes spp., Solenopsis spp., Technomyrmex, spp., Tetramorium spp.,Vespula spp., Vespa spp., and Xylocopa spp. A non-exhaustive list ofparticular species includes, but is not limited to, Atha/ia rosae, Attatexana, Ca/iroa cerasi, Cimbex americana, Iridomyrmex humilis,Linepithema humile, Mellifera Scutellata, Monomorium minimum, Monomoriumpharaonis, Neodiprion sertifer, Solenopsis invicta, Solenopsis geminata,Solenopsis molesta, Solenopsis richtery, Solenopsis xyloni, Tapinomasessile, and Wasmannia auropunctata.

(10) Order Isoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Coptotermes spp., Cornitermes spp.,Cryptotermes spp., Heterotermes spp., Kalotermes spp., Incisitermesspp., Macrotermes spp., Marginitermes spp., Microcerotermes spp.,Procomitermes spp., Reticulitermes spp., Schedorhinotermes spp., andZootermopsis spp. A non-exhaustive list of particular species includes,but is not limited to, Coptotermes acinaciformis, Coptotermescurvignathus, Coptotermes frenchi, Coptotermes formosanus, Coptotermesgestroi, Cryptotermes brevis, Heterotermes aureus, Heterotermes tenuis,Incisitermes minor, Incisitermes snyderi, Microtermes obesi,Nasutitermes corniger, Odontotermes formosanus, Odontotermes obesus,Reticulitermes banyulensis, Reticulitermes grassei, Reticulitermesflavipes, Reticulitermes hageni, Reticulitermes hesperus, Reticulitermessantonensis, Reticulitermes speratus, Reticulitermes tibialis, andReticulitermes virginicus.

(11) Order Lepidoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Adoxophyes spp., Agrotis spp.,Argyrotaenia spp., Cacoecia spp., Caloptilia spp., Chilo spp.,Chrysodeixis spp., Colias spp., Crambus spp., Diaphania spp., Diatraeaspp., Earias spp., Ephestia spp., Epimecis spp., Feltia spp., Gortynaspp., Helicoverpa spp., Heliothis spp., Indarbela spp., Lithocolletisspp., Loxagrotis spp., Malacosoma spp., Nemapogon spp., Peridroma spp.,Phyllonorycter spp., Pseudaletia spp., Plutella spp., Sesamia spp.,Spodoptera spp., Synanthedon spp., and Yponomeuta spp. A non-exhaustivelist of particular species includes, but is not limited to, Achaeajanata, Adoxophyes orana, Agrotis ipsilon, Alabama argillacea, Amorbiacuneana, Amyelois transitella, Anacamptodes defectaria, Anarsialineatella, Anomis sabulifera, Anticarsia gemmatalis, Archipsargyrospila, Archips rosana, Argyrotaenia citrana, Autographa gamma,Bonagota cranaodes, Borbo cinnara, Bucculatrix thurberiella, Capuareticulana, Carposina niponensis, Chlumetia transversa, Choristoneurarosaceana, Cnaphalocrocis medinalis, Conopomorpha cramerella, Corcyracephalonica, Cossus cossus, Cydia caryana, Cydia funebrana, Cydiamolesta, Cydia nigricana, Cydia pomonella, Darna diducta, Diaphanianitidalis, Diatraea saccharalis, Diatraea grandiosella, Earias insulana,Earias vittella, Ecdytolopha aurantianum, Elasmopalpus lignosellus,Ephestia cautella, Ephestia elutella, Ephestia kuehniella, Epinotiaaporema, Epiphyas postvittana, Erionota thrax, Estigmene acrea,Eupoecilia ambiguella, Euxoa auxiliaris, Galleria mellonella, Grapholitamolesta, Hedylepta indicata, Helicoverpa armigera, Helicoverpa zea,Heliothis virescens, Hellula undalis, Keiferia lycopersicella,Leucinodes orbonalis, Leucoptera coffeella, Leucoptera malifoliella,Lobesia botrana, Loxagrotis albicosta, Lymantria dispar, Lyonetiaclerkella, Mahasena corbetti, Mamestra brassicae, Manduca sexta, Marucatestulalis, Metisa plana, Mythimna unipuncta, Neoleucinodes elegantalis,Nymphula depunctalis, Operophtera brumata, Ostrinia nubilalis, Oxydiavesulia, Pandemis cerasana, Pandemis heparana, Papilio demodocus,Pectinophora gossypiella, Peridroma saucia, Perileucoptera coffeella,Phthorimaea operculella, Phyllocnistis citrella, Phyllonorycterblancardella, Pieris rapae, Plathypena scabra, Platynota idaeusalis,Plodia interpunctella, Plutella xylostella, Polychrosis viteana, Praysendocarpa, Prays oleae, Pseudaletia unipuncta, Pseudoplusia includens,Rachiplusia nu, Scirpophaga incertulas, Sesamia inferens, Sesamianonagrioides, Setora nitens, Sitotroga cerealella, Sparganothispilleriana, Spodoptera exigua, Spodoptera frugiperda, Spodopteraeridania, Thecla basilides, Tinea pellionella, Tineola bisselliella,Trichoplusia ni, Tuta absoluta, Zeuzera coffeae, and Zeuzea pyrina.

(12) Order Mallophaga. A non-exhaustive list of particular generaincludes, but is not limited to, Anaticola spp., Bovicola spp.,Chelopistes spp., Goniodes spp., Menacanthus spp., and Trichodectes spp.A non-exhaustive list of particular species includes, but is not limitedto, Bovicola bovis, Bovicola caprae, Bovicola ovis, Chelopistesmeleagridis, Goniodes dissimilis, Goniodes gigas, Menacanthusstramineus, Menopon gallinae, and Trichodectes canis.

(13) Order Orthoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Melanoplus spp. and Pterophylla spp. Anon-exhaustive list of particular species includes, but is not limitedto, Acheta domesticus, Anabrus simplex, Gryllotalpa africana,Gryllotalpa australis, Gryllotalpa brachyptera, Gryllotalpa hexadactyla,Locusta migratoria, Microcentrum retinerve, Schistocerca gregaria, andScudderia furcata.

(14) Order Psocoptera. A non-exhaustive list of particular speciesincludes, but is not limited to, Liposcelis decolor, Liposcelisentomophila, Lachesilla quercus, and Trogium pulsatorium.

(15) Order Siphonaptera. A non-exhaustive list of particular speciesincludes, but is not limited to, Ceratophyllus gallinae, Ceratophyllusniger, Ctenocephalides canis, Ctenocephalides felis, and Pulex irritans.

(16) Order Thysanoptera. A non-exhaustive list of particular generaincludes, but is not limited to, Caliothrips spp., Frankliniella spp.,Scirtothrips spp., and Thrips spp. A non-exhaustive list of particularspecies includes, but is not limited to, Caliothrips phaseoli,Frankliniella bispinosa, Frankliniella fusca, Frankliniellaoccidentalis, Frankliniella schultzei, Frankliniella tritici,Frankliniella williamsi, Heliothrips haemorrhoidalis, Rhipiphorothripscruentatus, Scirtothrips citri, Scirtothrips dorsalis, Taeniothripsrhopalantennalis, Thrips hawaiiensis, Thrips nigropilosus, Thripsorientalis, Thrips palmi, and Thrips tabaci.

(17) Order Thysanura. A non-exhaustive list of particular generaincludes, but is not limited to, Lepisma spp. and Thermobia spp.

(18) Order Acarina. A non-exhaustive list of particular genera includes,but is not limited to, Acarus spp., Aculops spp., Argus spp., Boophilusspp., Demodex spp., Dermacentor spp., Epitrimerus spp., Eriophyes spp.,Ixodes spp., Oligonychus spp., Panonychus spp., Rhizoglyphus spp., andTetranychus spp. A non-exhaustive list of particular species includes,but is not limited to, Acarapis woodi, Acarus siro, Aceria mangiferae,Aculops lycopersici, Aculus pelekassi, Aculus schlechtendali, Amblyommaamericanum, Brevipalpus obovatus, Brevipalpus phoenicis, Dermacentorvariabilis, Dermatophagoides pteronyssinus, Eotetranychus carpini,Liponyssoides sanguineus, Notoedres cati, Oligonychus coffeae,Oligonychus ilicis, Ornithonyssus bacoti, Panonychus citri, Panonychusulmi, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Rhipicephalussanguineus, Sarcoptes scabiei, Tegolophus perseaflorae, Tetranychusurticae, Tyrophagus longior, and Varroa destructor.

(19) Order Araneae. A non-exhaustive list of particular genera includes,but is not limited to, Loxosceles spp., Latrodectus spp., and Atrax spp.A non-exhaustive list of particular species includes, but is not limitedto, Loxosceles reclusa, Latrodectus mactans, and Atrax robustus.

(20) Class Symphyla. A non-exhaustive list of particular speciesincludes, but is not limited to, Scutigerella immaculata.

(21) Subclass Collembola. A non-exhaustive list of particular speciesincludes, but is not limited to, Bourletiella hortensis, Onychiurusarmatus, Onychiurus fimetarius, and Sminthurus viridis.

(22) Phylum Nematoda. A non-exhaustive list of particular generaincludes, but is not limited to, Aphelenchoides spp., Belonolaimus spp.,Criconemella spp., Ditylenchus spp., Globodera spp., Heterodera spp.,Hirschmanniella spp., Hoplolaimus spp., Meloidogyne spp., Pratylenchusspp., and Radopholus spp. A non-exhaustive list of particular speciesincludes, but is not limited to, Dirofilaria immitis, Globodera pallida,Heterodera glycines, Heterodera zeae, Meloidogyne incognita, Meloidogynejavanica, Onchocerca volvulus, Pratylenchus penetrans, Radopholussimilis, and Rotylenchulus reniformis.

(23) Phylum Mollusca. A non-exhaustive list of particular speciesincludes, but is not limited to, Arlon vulgaris, Cornu aspersum,Deroceras reticulatum, Limax flavus, Milax gagates, and Pomaceacanaliculata.

A particularly preferred pest group to control is sap-feeding pests.Sap-feeding pests, in general, have piercing and/or sucking mouthpartsand feed on the sap and inner plant tissues of plants. Examples ofsap-feeding pests of particular concern to agriculture include, but arenot limited to, aphids, leafhoppers, scales, thrips, psyllids,planthoppers, mealybugs, stinkbugs, and whiteflies. Specific examples ofOrders that have sap-feeding pests of concern in agriculture include butare not limited to, Anoplura and Hemiptera. Specific examples ofHemiptera that are of concern in agriculture include, but are notlimited to, Aulacaspis spp., Aphrophora spp., Aphis spp., Bemisia spp.,Coccus spp., Euschistus spp., Lygus spp., Macrosiphum spp., Nezara spp.,Rhopalosiphum spp., Sogatella spp., Nilaparvata spp., Laodelphax spp.,and Nephotettix spp.

Another particularly preferred pest group to control is chewing pests.Chewing pests, in general, have mouthparts that allow them to chew onthe plant tissue including roots, stems, leaves, buds, and reproductivetissues (including, but not limited to flowers, fruit, and seeds).Examples of chewing pests of particular concern to agriculture include,but are not limited to, caterpillars, beetles, grasshoppers, andlocusts. Specific examples of Orders that have chewing pests of concernin agriculture include but are not limited to, Coleoptera, Lepidoptera,and Orthoptera. Specific examples of Coleoptera that are of concern inagriculture include, but are not limited to, Anthonomus spp., Cerotomaspp., Chaetocnema spp., Colaspis spp., Cyclocephala spp., Diabroticaspp., Hypera spp., Phyllophaga spp., Phyllotreta spp., Sphenophorusspp., Sitophilus spp.

The phrase “pesticidally effective amount” means the amount of apesticide needed to achieve an observable effect on a pest, for example,the effects of necrosis, death, retardation, prevention, removal,destruction, or otherwise diminishing the occurrence and/or activity ofa pest in a locus. This effect may come about when pest populations arerepulsed from a locus, pests are incapacitated in, or around, a locus,and/or pests are exterminated in, or around, a locus. Of course, acombination of these effects can occur. Generally, pest populations,activity, or both are desirably reduced more than fifty percent,preferably more than 90 percent, and most preferably more than 99percent. In general, a pesticidally effective amount, for agriculturalpurposes, is from about 0.0001 grams per hectare to about 5000 grams perhectare, preferably from about 0.0001 grams per hectare to about 500grams per hectare, and it is even more preferably from about 0.0001grams per hectare to about 50 grams per hectare. Alternatively, about150 grams per hectare to about 250 grams per hectare may be used againstpests.

Detailed Description of this Disclosure

This document discloses the moleculeN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfonyl)propanamide:

Formula One Also Known as F1

Formula One may exist in different geometric or optical isomeric ordifferent tautomeric forms. One or more centers of chirality may bepresent, in which case Formula One may be present as pure enantiomers,mixtures of enantiomers, pure diastereomers or mixtures ofdiastereomers. It will be appreciated by those skilled in the art thatone stereoisomer may be more active than the other stereoisomers.Individual stereoisomers may be obtained by known selective syntheticprocedures, by conventional synthetic procedures using resolved startingmaterials, or by conventional resolution procedures. Centers oftautomerisation may be present. This disclosure covers all such isomers,tautomers, and mixtures thereof, in all proportions. The structuresdisclosed in the present disclosure maybe drawn in only one geometricform for clarity, but are intended to represent all geometric forms ofthe molecule.

Synthesis of Formula One (F1)

Starting materials, reagents, and solvents that were obtained fromcommercial sources were used without further purification. Anhydroussolvents were purchased as Sure/Seal™ from Aldrich and were used asreceived. Melting points were obtained on a Thomas Hoover Unimeltcapillary melting point apparatus or an OptiMelt Automated Melting PointSystem from Stanford Research Systems and are uncorrected. Examplesusing “room temperature” were conducted in climate controlledlaboratories with temperatures ranging from about 20° C. to about 24° C.Molecules are given their known names, named according to namingprograms within ISIS Draw, ChemDraw, or ACD Name Pro. If such programsare unable to name a molecule, such molecule is named using conventionalnaming rules. ¹H NMR spectral data are in ppm (δ) and were recorded at300, 400, 500, or 600 MHz; ¹³C NMR spectral data are in ppm (δ) and wererecorded at 75, 100, or 150 MHz; and ¹⁹F NMR spectral data are in ppm(δ) and were recorded at 376 MHz, unless otherwise stated.

A person skilled in the art will recognize that it may be possible toachieve the synthesis of desired molecules by performing some of thesteps of the synthetic routes in a different order to that described. Aperson skilled in the art will also recognize that it may be possible toperform standard functional group interconversions or substitutionreactions on desired molecules to introduce or modify substituents.

Example 1: Preparation of 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine(C5)

Step 1—Preparation of 3-chloro-1H-pyrazol-4-amine hydrochloride (C2): A2 liter (L) three-necked round bottom flask was affixed with an overheadstirrer, a temperature probe, an addition funnel, and a nitrogen inlet.Into this three-necked flask were added ethanol (600 milliliters (mL))and 4-nitro-1H-pyrazole (C1; 50.6 grams (g), 447 millimoles (mmol)). Tothis solution was added, in one portion, concentrated hydrochloric acid(HCl; 368 mL) (note: rapid exotherm from 15° C. to 39° C.), and theresulting mixture was purged with nitrogen (N₂) for 5 minutes (min).Palladium on alumina (5% w/w) (2.6 g) was added, and the mixture wasstirred at room temperature while triethylsilane (208 g, 1789 mmol) wasadded drop-wise over 4 hours (h). The reaction mixture, which started toself-heat slowly from 35° C. to 55° C. over 2 h, was stirred for a totalof 16 h. The mixture was vacuum filtered through a plug of Celite®, anda biphasic mixture was collected. The biphasic mixture was transferredto a separatory funnel, and the bottom aqueous layer was collected androtary evaporated (60° C., 50 mmHg) to dryness with the aid ofacetonitrile (3×350 mL). The resulting yellow solid was suspended inacetonitrile (150 mL) and allowed to stand for 2 h at room temperaturefollowed by 1 h at 0° C. in the refrigerator. The solids were filteredand washed with acetonitrile (100 mL) to afford the title compound as awhite solid (84 g, 97% yield, 80% purity): mp 190-193° C.; ¹H NMR (400MHz, DMSO-d₆) δ 10.46-10.24 (br s, 2H), 8.03 (s, 0.54H), 7.75 (s,0.46H), 5.95 (br s, 1H); ¹³C-NMR (101 MHz, DMSO-d₆) δ 128.24, 125.97,116.71.

Step 2—Preparation of tert-butyl (3-chloro-1H-pyrazol-4-yl)carbamate(C3): Into a 2 L round bottom flask were added3-chloro-1H-pyrazol-4-amine hydrochloride (C2; 100 g, 649 mmol) andtetrahydrofuran (THF; 500 mL). To this mixture were added sequentiallydi-tert-butyl dicarbonate (156 g, 714 mmol), sodium bicarbonate (120 g,1429 mmol) and water (50.0 mL). The mixture was stirred for 16 h,diluted with water (500 mL) and ethyl acetate (EtOAc; 500 mL) andtransferred to a separatory funnel. This gave three layers: a) bottomlayer—white gelatinous precipitate; b) middle layer—light yellow aqueousliquid; and c) top layer—auburn organic liquid. The phases wereseparated, collecting the bottom and middle layers (i.e., aqueous phase)together. The aqueous phase was extracted with EtOAc (2×200 mL), and theorganic extracts were combined, washed with brine (200 mL), dried overanhydrous sodium sulfate, filtered and concentrated by rotaryevaporation to give a thick auburn-colored oil (160 g). The thick oilwas suspended in hexane (1000 mL) and stirred at 55° C. for 2 h. Thisgave a light brown suspension. The mixture was cooled to 0° C., and thesolid was collected by vacuum filtration and rinsed with hexane (2×10mL). The sample was air dried to constant mass to afford the titlecompound as a light brown solid (103 g, 72% yield, 80% purity): mp137-138° C.; ¹H NMR (400 MHz, CDCl₃) δ 10.69 (s, 1H), 7.91 (s, 1H), 1.52(s, 9H).

Step 3—Preparation of tert-butyl(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (C4): A dry 2 Lthree-necked round bottom flask was equipped with a mechanical stirrer,nitrogen inlet, thermometer, and reflux condenser. Into this flask wereadded 3-iodopyridine (113 g, 551 mmol), tert-butyl(3-chloro-1H-pyrazol-4-yl)carbamate (C3; 100 g, 459 mmol), powderedpotassium phosphate (195 g, 919 mmol), and copper chloride (3.09 g, 23mmol). Acetonitrile (1 L) and N¹,N²-dimethylethane-1,2-diamine (101 g,1149 mmol) were added sequentially, and the mixture was heated to 81° C.for 4 h. The mixture was cooled to room temperature and filtered througha bed of Celite®. The filtrate was transferred to a 4 L Erlenmeyer flaskequipped with a mechanical stirrer and diluted with water until thetotal volume was about 4 L. The mixture was stirred for 30 min at roomtemperature and the resulting solid was collected by vacuum filtration.The solid was washed with water and oven dried for several days in vacuoat 40° C. to a constant weight to give the title compound as a tan solid(117.8 g, 87% yield, 80% purity): mp 140-143° C.; ¹H NMR (400 MHz,CDCl₃) δ 8.96 (s, 1H), 8.53 (dd, J=4.7, 1.2 Hz, 1H), 8.36 (s, 1H), 7.98(ddd, J=8.3, 2.7, 1.4 Hz, 1H), 7.38 (dd, J=8.3, 4.8 Hz, 1H), 6.37 (s,1H), 1.54 (s, 9H); ESIMS m/z 338 ([M-t-Bu]⁺), 220 ([M-O-t-Bu]⁻).

Step 4—Preparation of 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (C5):Trifluoroacetic acid (TFA; 6.79 mL) was added to tert-butyl(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)carbamate (C4; 2 g, 6.79mmol) in dichloromethane (DCM; 6.79 mL), and the mixture was stirred atroom temperature for 2 h. Toluene (12 mL) was added, and the reactionmixture was concentrated in vacuo to near dryness. The concentratedreaction mixture was poured into a separatory funnel containingsaturated aqueous sodium bicarbonate and was extracted with DCM (3×10mL). The combined organic layers were concentrated to give the titlecompound as a white solid (0.954 g, 72%): mp 137.9-139.9° C.; ¹H NMR(400 MHz, CDCl₃) δ 8.84 (d, J=2.4 Hz, 1H), 8.50 (dd, J=4.7, 1.4 Hz, 1H),7.95 (ddd, J=8.3, 2.7, 1.5 Hz, 1H), 7.52 (s, 1H), 7.37 (ddd, J=8.4, 4.7,0.7 Hz, 1H), 3.18 (s, 2H); ESIMS m/z 196 ([M+H]⁺).

Example 2: Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfonyl)propanamide(Formula One)

Step 1—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylthio)propanamide(C7): To a suspension of 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine(C5; 0.1 g, 0.514 mmol) and 2-(methylthio)propanoic acid (C6; 0.185 g,1.541 mmol) in DCM (1.713 mL) were added sequentiallyN,N-dimethylpyridin-4-amine (0.220 g, 1.798 mmol) andN1-((ethylimino)methylene)-N3,N3-dimethylpropane-1,3-diaminehydrochloride (0.305 g, 1.593 mmol). The reaction mixture was stirred atambient temperature for 18 h and was concentrated. Purification bysilica gel chromatography (0-100% EtOAc/hexanes) gave the title compoundas a white solid (116 mg, 72%): mp 129-132° C.; ¹H NMR (400 MHz, CDCl₃)δ 8.98 (d, J=2.4 Hz, 1H), 8.63 (s, 1H), 8.58-8.53 (m, 1H), 8.03-7.96 (m,1H), 7.43-7.37 (m, 1H), 3.59-3.48 (m, 1H), 2.18 (s, 3H), 1.59 (d, J=7.3Hz, 3H); ESIMS m/z 297 ([M+1]⁺).

Step 2—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfonyl)propanamide(Formula One): To a 100 mL round bottom flask were addedN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylthio)propanamide(C7; 882 mg, 2.97 mmol), acetic acid (6.0 mL), and sodium perboratetetra hydrate (915 mg, 5.94 mmol). The reaction mixture was stirredovernight under inert atmosphere in a heating block warmed to 50° C. Thereaction mixture was then poured into a brine solution and extractedwith DCM (3×20 mL). The combined organic extracts were dried overmagnesium sulfate, filtered and concentrated. Purification of theresulting residue by silica gel chromatography (0-10% methanol in DCM)gave the title compound as a white foam (734 mg, 74%): ¹H NMR (400 MHz,DMSO-d₆) δ 10.41 (s, 1H), 9.07 (d, J=2.7 Hz, 1H), 8.94 (s, 1H), 8.55(dd, J=4.7, 1.4 Hz, 1H), 8.23 (ddd, J=8.4, 2.8, 1.4 Hz, 1H), 7.55 (ddd,J=8.4, 4.8, 0.7 Hz, 1H), 4.41 (q, J=7.0 Hz, 1H), 3.07 (s, 3H), 1.57 (d,J=7.1 Hz, 3H); ESIMS m/z 329 ([M+H]⁺); IR (thin film) 1680 cm⁻¹.

Synthesis of Comparative Molecules Example 3: Preparation of3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (C9)

Step 1—Preparation of tert-butyl(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)(methyl)carbamate (C8): To asolution of tert-butyl3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-ylcarbamate (C4; 1.0 g, 3.39mmol) in N,N-dimethylformamide (16.96 mL) at 0° C. was added sodiumhydride (0.163 g, 4.07 mmol). After 30 min the flask was warmed toambient temperature and the reaction mixture was stirred for another 30min. Iodomethane (0.232 mL, 3.73 mmol) was added to the flask, and thereaction mixture was stirred at ambient temperature for 2 h. Thereaction was quenched by adding saturated ammonium chloride. Thereaction mixture was extracted twice with tert-butyl methyl ether. Theorganic layer was dried over sodium sulfate, filtered and concentrated.Purification via silica column chromatography (0-100% EtOAc/hexanes)gave the title compound as a yellow oil (983 mg, 94%): ¹H NMR (400 MHz,CDCl₃) δ 8.91 (d, J=2.5 Hz, 1H), 8.64-8.48 (m, 1H), 8.01 (d, J=7.5 Hz,1H), 7.90 (s, 1H), 7.41 (dd, J=8.3, 4.8 Hz, 1H), 3.23 (s, 3H), 1.58-1.25(m, 9H); ESIMS m/z 309 ([M+H]⁺); IR (thin film) 1693 cm⁻¹.

Step 2—Preparation of3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (C9): Totert-butyl 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl(methyl)carbamate(C8; 1.65 g, 5.34 mmol) in DCM (5.4 mL) was added trifluoroacetic acid(TFA; 5.4 mL) and the solution was stirred at room temperature for 1 h.Toluene was added and the reaction mixture was concentrated in vacuo tonear dryness. The concentrated reaction mixture was poured into aseparatory funnel containing saturated sodium bicarbonate and themixture was extracted with EtOAc (3×20 mL). The extracts were combined,dried over magnesium sulfate, filtered, and concentrated to dryness. Thetitle compound was isolated as a pale yellow solid (0.92 g, 83%): mp108-118° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.88 (d, J=2.4 Hz, 1H), 8.48 (dd,J=4.7, 1.4 Hz, 1H), 7.96 (ddd, J=8.3, 2.7, 1.4 Hz, 1H), 7.41-7.29 (m,2H), 2.87 (s, 3H); EIMS m/z 208.

Example 4: Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(methylsulfonyl)propanamide(Comparative Example 1 also known as CE1)

Step 1—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(methylthio)propanamide(C10): To a solution of 2-(methylthio)propanoic acid (C6; 481 mg, 4.00mmol) in DCM (6 mL) were added oxalyl dichloride (0.384 mL, 4.40 mmol)and one drop of dimethylformamide. Vigorous bubbling was observed, andstirring was continued for 30 minutes. The crude acyl chloride reactionmixture (C6b) was concentrated in vacuo to near dryness. Theconcentrated reaction mixture (C6b) was dissolved in DCM (3 mL) and wasadded slowly (over ˜5 min) to an ice-cold solution of3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (C9; 417 mg, 2mmol) and N-ethyl-N-isopropylpropan-2-amine (0.751 mL, 4.40 mmol) in DCM(3 mL). The resulting deep orange solution was slowly warmed to roomtemperature over 0.5 hour and was stirred at ambient temperature for 1.5hour. The reaction mixture was quenched by the addition of saturatedsodium bicarbonate solution. The reaction mixture was extracted with DCM(3×10 mL). Purification of the residue by silica gel chromatography(0-100% EtOAc/hexane) gave the title compound as a white solid (495 mg,76%): mp 128-133° C.; ¹H NMR (400 MHz, CDCl₃) δ 8.94 (d, J=2.4 Hz, 1H),8.62 (d, J=3.8 Hz, 1H), 8.15 (s, 1H), 8.03 (d, J=8.3 Hz, 1H), 7.46 (dd,J=8.3, 4.8 Hz, 1H), 3.34 (q, J=6.8 Hz, 1H), 3.26 (s, 3H), 2.10 (s, 3H),1.45 (d, J=6.9 Hz, 3H); ESIMS m/z 311 ([M+1]⁺).

Step 2—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(methylsulfonyl)propanamide(Comparative Example 1): To a 20 mL vial were added sequentiallyN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(methylthio)propanamide(C10; 306 mg, 0.985 mmol), acetic acid (2 mL), and sodium perboratetetrahydrate (333 mg, 2.17 mmol). The solution was heated at 65° C. for3 h, cooled, and quenched by the slow addition of saturated sodiumbicarbonate solution. The solution was extracted with DCM (3×10 mL), andthe combined organic extracts were dried, and concentrated. Purificationof the resulting mixture by silica gel chromatography (0-10% methanol inDCM) gave the title compound as an off-white solid (221 mg, 62%): ¹H NMR(400 MHz, CDCl₃) δ 8.97 (dd, J=2.7, 0.7 Hz, 1H), 8.64 (dd, J=4.7, 1.5Hz, 1H), 8.22 (s, 1H), 8.00 (ddd, J=8.4, 2.7, 1.5 Hz, 1H), 7.45 (ddd,J=8.4, 4.8, 0.8 Hz, 1H), 4.14-3.94 (m, 1H), 3.33 (s, 3H), 3.02 (d, J=0.8Hz, 3H), 1.65 (d, J=7.0 Hz, 3H); ESIMS m/z 343 ([M+1]⁺); IR (thin film)1657 cm⁻¹.

Example 5: Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(methylsulfonyl)acetamide(Comparative Example 2 also known as CE2)

Step 1—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(methylthio)acetamide(C12): To a 20 mL vial were added sequentially3-chloro-N-methyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine (C9; 417 mg, 2mmol), 2-(methylthio)acetic acid (C11; 318 mg, 3 mmol),N1-((ethylimino)methylene)-N3,N3-dimethylpropane-1,3-diaminehydrochloride (767 mg, 4 mmol), N,N-dimethylpyridin-4-amine (611 mg, 5mmol), and dichloroethane (6 mL). The solution was stirred at roomtemperature for 18 h and concentrated. Purification by silica gelchromatography (0-100% EtOAc/hexanes) provided the title compound aspale yellow oil (517 mg, 83%): ¹H NMR (400 MHz, CDCl₃) δ 8.95 (d, J=2.5Hz, 1H), 8.62 (dd, J=4.8, 1.4 Hz, 1H), 8.13 (s, 1H), 8.04 (ddd, J=8.3,2.7, 1.4 Hz, 1H), 7.50-7.43 (m, 1H), 3.26 (s, 3H), 3.12 (s, 2H), 2.24(s, 3H); 13C NMR (101 MHz, CDCl₃) δ 170.00, 148.61, 140.15, 140.03,135.68, 126.56, 126.42, 125.33, 124.15, 37.16, 34.94, 16.22; ESIMS m/z297 ([M+H]⁺).

Step 2—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(methylsulfonyl)acetamide(Comparative Example 2): To a 7 mL vial were added sequentiallyN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-methyl-2-(methylthio)acetamide(C12; 262 mg, 0.883 mmol), acetic acid (1.5 mL), and sodium perboratetetrahydrate (299 mg, 1.942 mmol). The mixture was stirred at 65° C. for2 h, then quenched by the addition of saturated sodium bicarbonatesolution. The reaction mixture was extracted with DCM (3×10 mL). Thecombined organic extracts were dried and concentrated. Purification ofthe resulting mixture by silica gel chromatography (0-10% methanol inDCM) afforded the title compound as a white semi-solid (192 mg, 62.8%):¹H NMR (500 MHz, CDCl₃) δ 8.97 (d, J=2.6 Hz, 1H), 8.64 (dd, J=4.9, 1.3Hz, 1H), 8.24 (s, 1H), 8.00 (ddd, J=8.4, 2.8, 1.4 Hz, 1H), 7.45 (dd,J=8.4, 4.8 Hz, 1H), 3.96 (s, 2H), 3.33 (s, 3H), 3.20 (s, 3H); ESIMS m/z329 ([M+H]⁺); IR (thin film) 1664 cm⁻¹.

Example 6: Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfonyl)acetamide(Formula Two also known as CE3)

Step 1—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylthio)acetamide(C14): To a suspension of 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine(C5; 1.0 g, 5.14 mmol), N,N-dimethylpyridin-4-amine (628 mg, 5.14 mmol),and 2-(methylthio)acetic acid (C13; 654 mg, 6.17 mmol) in dichloroethane(6 mL) was addedN1-((ethylimino)methylene)-N3,N3-dimethylpropane-1,3-diaminehydrochloride (1.477 mg, 7.71 mmol). The reaction mixture was stirred atambient temperature for 24 h. The mixture was diluted with DCM andwashed with saturated aqueous ammonium chloride and brine, dried overmagnesium sulfate, and concentrated in vacuo to give a brown gum.Purification of the gum by silica gel chromatography (DCM-methanol) gavethe title compound as a white solid (1.268 g, 87%): ¹H NMR (400 MHz,CDCl₃) δ 9.06-8.90 (m, 1H), 8.74 (s, 1H), 8.64 (s, 1H), 8.57-8.45 (m,1H), 8.05-7.90 (m, 1H), 7.46-7.33 (m, 1H), 3.41 (s, 2H), 2.24 (s, 3H);ESIMS m/z 283 ([M+H]⁺).

Step 2—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfonyl)acetamide(Formula Two): To solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylthio)acetamide(C14; 160 mg, 0.566 mmol) in acetic acid (1.5 mL) was added sodiumperborate tetrahydrate (183 mg, 1.188 mmol). The reaction mixture wasstirred at 60° C. for 2 h. The reaction mixture was cooled and thenpoured into an excess amount of saturated sodium bicarbonate solutionand extracted with DCM. Purification of the resulting residue by silicagel chromatography (0-10% methanol in DCM) gave the title compound as awhite solid (101 mg, 53.9%) andN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfinyl)acetamide(C15) as a white solid (40 mg, 22.5%).

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfonyl)acetamide(Formula Two): ¹H NMR (300 MHz, CDCl₃) δ 8.95 (dd, J=2.7, 0.8 Hz, 1H),8.66 (d, J=0.6 Hz, 1H), 8.53 (dd, J=4.8, 1.4 Hz, 1H), 8.04 (ddd, J=8.4,2.7, 1.4 Hz, 1H), 7.45 (ddd, J=8.3, 4.8, 0.7 Hz, 1H), 4.23 (q, J=0.8 Hz,2H), 3.21 (t, J=0.8 Hz, 3H); ESIMS m/z 315 ([M+H]⁺); IR (thin film) 1677cm⁻¹.

N-(3-Chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfinyl)acetamide(C15): ¹H NMR (300 MHz, CDCl₃) δ 8.95 (dd, J=2.7, 0.8 Hz, 1H), 8.65 (d,J=0.7 Hz, 1H), 8.53 (dd, J=4.8, 1.4 Hz, 1H), 8.04 (ddd, J=8.4, 2.7, 1.5Hz, 1H), 7.45 (ddd, J=8.4, 4.8, 0.8 Hz, 1H), 3.93 (d, J=13.9 Hz, 1H),3.71 (d, J=13.8 Hz, 1H), 2.80 (s, 3H); ESIMS m/z 299 ([M+H]⁺); IR (thinfilm) 1673 cm⁻¹.

Example 7: Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-(methylsulfonyl)acetamide(Formula Three also known as CE4)

Step 1—Preparation of 2-methyl-2-(methylthio)propanoyl chloride (C17): A100 mL round bottom flask was charged with ethyl2-methyl-2-(methylthio)propanoate (C16; 500 mg, 3.08 mmol), lithiumhydroxide hydrate (400 mg, 9.53 mmol), THF (6.0 mL), methanol (2.0 mL)and water (2.0 mL). The reaction mixture was allowed to stir at roomtemperature overnight. The reaction mixture was made acidic with 2normal (N) HCl and was extracted with EtOAc (3×15 mL). The combinedorganic extracts were dried over magnesium sulfate, filtered andconcentrated.

The title compound can be prepared from the acid above as in Liu,Aiping; Ren, Yeguo; Huang, Lu; Pei, Hui; Hu, Zhibin; Lin, Xuemei; Cheng,Sixi; Huang, Mingzhi; Zhu, Xiaoxing; Wei, Tianlong CN 101928271, 2010.It was isolated (without purification) as a colorless solid (394 mg,83%): ¹H NMR (500 MHz, DMSO-d₆) δ 2.05 (s, 3H), 1.39 (s, 6H); 13C NMR(126 MHz, DMSO-d₆) δ 174.01, 45.08, 24.31, 11.73; IR (thin film) 3394,1652, 1204, 1040, 1024, 995 cm⁻¹.

Step 2—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-methyl-2-(methylthio)propanamide(C18): A 50-mL round bottom flask was charged with2-methyl-2-(methylthio)propanoyl chloride from Step 1 (C17; 200 mg,1.310 mmol), 3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-amine (C5; 255 mg,1.310 mmol) and dichloroethane (6.552 mL).N-Ethyl-N-isopropylpropan-2-amine (456 μL, 2.62 mmol) was added underinert atmosphere. The reaction mixture was allowed to stir at roomtemperature for 3 h and was concentrated. The reaction was quenched bypouring into a brine solution, and the reaction mixture was extractedwith DCM (2×15 mL). The combined organic extracts were dried overmagnesium sulfate, filtered and concentrated. Purification of theresulting residue by silica gel chromatography (0-80% EtOAc/hexanes)gave the title compound as a light orange residue (191 mg, 46.4%): ¹HNMR (400 MHz, DMSO-d₆) δ 9.37 (s, 1H), 9.07 (dd, J=2.8, 0.7 Hz, 1H),8.78 (s, 1H), 8.55 (dd, J=4.7, 1.4 Hz, 1H), 8.22 (ddd, J=8.3, 2.7, 1.4Hz, 1H), 7.56 (ddd, J=8.4, 4.8, 0.8 Hz, 1H), 2.10 (s, 3H), 1.53 (s, 6H);13C NMR (126 MHz, DMSO-d₆) δ 171.99, 147.05, 138.78, 136.62, 134.86,125.02, 124.85, 123.72, 119.01, 47.13, 24.99, 11.65; IR (thin film)1675, 1484, 1388, 1353, 947, 800, 702 cm⁻¹; ESIMS m/z 311 ([M+H]⁺).

Step 3—Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-methyl-2-(methylsulfonyl)propanamide(Formula Three): A 25 mL vial was charged withN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-2-methyl-2-(methylthio)propanamide(C18; 75 mg, 0.241 mmol), sodium perborate tetrahydrate (74 mg, 0.483mmol), and acetic acid (2.0 mL) was added. The reaction mixture wasstirred in a heating block at 50° C. for 3 h. The reaction mixture wasdiluted with water (7 mL) and was extracted with DCM (3×7 mL). Thecombined organic extracts were dried over magnesium sulfate, filtered,and concentrated. Purification of the resulting residue by silica gelchromatography (0-75% EtOAc/hexanes) provided the title compound as awhite solid (47 mg, 56.2%): ¹H NMR (400 MHz, DMSO-d₆) δ 9.50 (s, 1H),9.07 (d, J=2.6 Hz, 1H), 8.83 (s, 1H), 8.56 (dd, J=4.7, 1.4 Hz, 1H), 8.23(ddd, J=8.4, 2.8, 1.4 Hz, 1H), 7.68-7.49 (m, 1H), 3.10 (s, 3H), 1.66 (s,6H); 13C NMR (101 MHz, DMSO-d₆) δ 167.92, 148.27, 139.99, 137.59,135.89, 126.34, 126.09, 124.77, 119.33, 67.49, 36.97, 19.76; IR (thinfilm) 1678, 1292, 1108, 946, 800, 701 cm⁻¹; ESIMS m/z 343 ([M+H]⁺).

Biological Assays

The following bioassays were conducted against Green Peach Aphid (Myzuspersicae) and Sweetpotato Whitefly (Bemisia tabaci), which are goodindicator species for a broad range of sap-feeding pests. The resultswith these two indicator species show the broad usefulness of theFormula One in controlling sap-feeding insects.

Test Solutions:

F1, CE1, CE2, CE3, and CE4 (2 mg each) were each dissolved in 2 mL ofacetone/methanol (1:1) solvent, forming stock solutions of 1000 ppm foreach test molecule. The stock solutions were diluted 5× with 0.025%Tween® 20 in water to obtain test solutions at 200 ppm for each testmolecule. Subsequent 4× dilutions, in water containing 0.025% Tween® 20and 10% acetone/methanol (1:1), were used to generate the desiredconcentrations for dose responses. A minimum of 5 concentrations of eachtest molecule were used for each assay.

Bioassay 1: Green Peach Aphid (Myzus persicae, MYZUPE) (“GPA”).

GPA is the most significant aphid pest of peach trees, causing decreasedgrowth, shriveling of the leaves, and the death of various tissues. Itis also hazardous because it acts as a vector for the transport of plantviruses, such as potato virus Y and potato leafroll virus to members ofthe nightshade/potato family Solanaceae, and various mosaic viruses tomany other food crops. GPA attacks such plants as broccoli, burdock,cabbage, carrot, cauliflower, daikon, eggplant, green beans, lettuce,macadamia, papaya, peppers, sweet potatoes, tomatoes, watercress, andzucchini, among other crops. GPA also attacks many ornamental crops suchas carnation, chrysanthemum, flowering white cabbage, poinsettia, androses. GPA has developed resistance to many pesticides. Currently, it isa pest that has the third largest number of reported cases of insectresistance (Sparks et al.). Consequently, because of the above factorscontrol of this pest is important. Furthermore, molecules that controlthis pest (GPA), which is known as a sap-feeding pest, are useful incontrolling other pests that feed on the sap from plants.

Test solutions of Formula One and the Comparative Examples, prepared asdescribed above, were tested against GPA using the following procedure.

Cabbage seedlings grown in 3-inch pots, with 2-3 small (3-5 cm) trueleaves, were used as test substrate. The seedlings were infested with20-50 GPA (wingless adult and nymph stages) one day prior to chemicalapplication. Four pots with individual seedlings were used for eachtreatment. A hand-held aspirator-type sprayer was used for spraying asolution to both sides of cabbage leaves until runoff. Reference plants(solvent check) were sprayed with the diluent only (0.025% Tween® 20 and10% acetone/methanol (1:1) in water). Treated plants were held in aholding room for three days at approximately 25° C. and ambient relativehumidity (RH) prior to grading. Evaluation was conducted by counting thenumber of live aphids per plant under a microscope three days aftertreatment. Percent control was measured using Abbott's correctionformula (W. S. Abbott, “A Method of Computing the Effectiveness of anInsecticide” J. Econ. Entomol. 18 (1925), pp. 265-267) as follows:

Corrected % Control=100*(X−Y)/X

where X=No. of live aphids on solvent check plants and Y=No. of liveaphids on treated plants. The results are given in Table 2 below.Bioassay 2: Sweetpotato Whitefly (Bemisia tabaci, BEMITA) (“SPW”).

Sweetpotato Whitefly is a major destructive pest to cotton. It is also aserious pest to many vegetable crops, such as melons, cole crops,tomatoes, and head lettuce, as well as ornamental plants. SPW causesdamage both through direct feeding damage and virus transmission. SPW isa sap-feeding insect, and its feeding removes nutrients from the plant.This may result in stunted growth, defoliation, reduced yields, and bollshed in cotton. SPW produces large quantities of honeydew, whichsupports the growth of sooty molds on the plant leaves. SPW is also avector for viruses, such as cotton leaf crumple virus and tomato yellowleaf curl virus.

Test solutions of Formula One and the Comparative Examples, prepared asdescribed above, were tested against SPW using the following procedure.

Cotton seedlings grown in 3-inch pots, pruned so that only one true leafremained, were used as test substrate. Adult B. tabaci were allowed tocolonize these plants and lay eggs for 24 hours after which all adultswere removed from the plants using compressed air. Plants were monitoredfor egg development and, when crawler emergence was underway (>25%emergence based on visual examination using a microscope), the plantswere sprayed using the test solutions and methods described above forgreen peach aphids (GPA). Treated plants were held in a holding room atapproximately 25° C. and ambient relative humidity (RH) prior tograding. Evaluation was conducted by counting the number of developed2-3 instar nymphs per plant under a microscope 7-9 days after treatment.Percent control was measured using Abbott's correction formula (W. S.Abbott, “A Method of Computing the Effectiveness of an Insecticide” J.Econ. Entomol. 18 (1925), pp. 265-267) as follows:

Corrected % Control=100*(X−Y)/X

where X=No. of live nymphs on solvent check plants and Y=No. of livenymphs on treated plants. The results are given in Table 2 below.

Analysis of Bioassays

TABLE TWO Bemisia tabaci Myzus persicae Molecule # Mean LC₅₀ PPM % #Mean LC₅₀ PPM % CE1 2 5.61 15 2 0.29 314 CE2 1 21.01 331 2 0.52 643 F1 24.87 6 0.07 CE3 2 25.35 421 3 0.05 −29 CE4 2 9.72 100 2 2.17 3000

In Table 2, F1, CE1, CE2, CE3, and CE4, bioassay results are shown. The#column shows the number of replicates of each bioassay conducted. TheMean LC₅₀ indicates parts per million. The % column shows the percentincrease in the Mean LC₅₀ required. For example, in the Myzus persicaebioassays, comparing CE4 to F1, the percent increase is((2.17-0.07)/0.07)*100=3000% which means it take much more of CE4compared to F1 in order to achieve the same effect.

In light of the above bioassays, the average % of all of the bioassaysis ((15+331+421+100+314+643+(−29)+3000)/8) which is about 599%. Thisindicates that on average about 599% more pesticide is require in orderto be as effective as F1. This is unexpected considering the moleculestested.

Agriculturally Acceptable Acid Addition Salts, Salt Derivatives,Solvates, Ester Derivatives, Polymorphs, Isotopes, and Radionuclides

Formula One may be formulated into agriculturally acceptable acidaddition salts. By way of a non-limiting example, an amine function canform salts with hydrochloric, hydrobromic, sulfuric, phosphoric, acetic,benzoic, citric, malonic, salicylic, malic, fumaric, oxalic, succinic,tartaric, lactic, gluconic, ascorbic, maleic, aspartic, benzenesulfonic,methanesulfonic, ethanesulfonic, hydroxyl-methanesulfonic, andhydroxyethanesulfonic acids.

Formula One may be formulated into salt derivatives. By way of anon-limiting example, a salt derivative may be prepared by contacting afree base with a sufficient amount of the desired acid to produce asalt. A free base may be regenerated by treating the salt with asuitable dilute aqueous base solution such as dilute aqueous sodiumhydroxide, potassium carbonate, ammonia, and sodium bicarbonate. As anexample, in many cases, a pesticide such as 2,4-D is made morewater-soluble by converting it to its dimethylamine salt.

Formula One may be formulated into stable complexes with a solvent, suchthat the complex remains intact after the non-complexed solvent isremoved. These complexes are often referred to as “solvates.” However,it is particularly desirable to form stable hydrates with water as thesolvent.

Formula One may be made as various crystal polymorphs. Polymorphism isimportant in the development of agrochemicals since different crystalpolymorphs or structures of the same molecule can have vastly differentphysical properties and biological performances.

Formula One may be made with different isotopes. Of particularimportance are molecules having ²H (also known as deuterium) or ³H (alsoknown as tritium) in place of ¹H. Formula One may be made with differentradionuclides. Of particular importance are molecules having ¹⁴C (alsoknown as radiocarbon). Formula One having deuterium, tritium, or ¹⁴C maybe used in biological studies allowing tracing in chemical andphysiological processes and half-life studies, as well as, MoA studies.

Combinations

In another embodiment of this invention, Formula One may be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more active ingredients.

In another embodiment of this invention, Formula One may be used incombination (such as, in a compositional mixture, or a simultaneous orsequential application) with one or more active ingredients each havinga MoA that is the same as, similar to, or, preferably, different from,the MoA of Formula One.

In another embodiment, Formula One may be used in combination (such as,in a compositional mixture, or a simultaneous or sequential application)with one or more molecules having acaricidal, algicidal, avicidal,bactericidal, fungicidal, herbicidal, insecticidal, molluscicidal,nematicidal, rodenticidal, and/or virucidal properties.

In another embodiment, Formula One may be used in combination (such as,in a compositional mixture, or a simultaneous or sequential application)with one or more molecules that are antifeedants, bird repellents,chemosterilants, herbicide safeners, insect attractants, insectrepellents, mammal repellents, mating disrupters, plant activators,plant growth regulators, plant health stimulators or promoters,nitrification inhibitors, and/or synergists.

In another embodiment, Formula One may also be used in combination (suchas in a compositional mixture, or a simultaneous or sequentialapplication) with one or more biopesticides.

In another embodiment, in a pesticidal composition combinations ofFormula One and an active ingredient may be used in a wide variety ofweight ratios. For example, in a two-component mixture, the weight ratioof Formula One to an active ingredient, the weight ratios in Table 3 maybe used. However, in general, weight ratios less than about 10:1 toabout 1:10 are preferred.

TABLE 3 Weight Ratios Formula One:active ingredient 100:1 to 1:100 50:1to 1:50 20:1 to 1:20 10:1 to 1:10 5:1 to 1:5 3:1 to 1:3 2:1 to 1:2 1:1

Weight ratios of a molecule of Formula One to an active ingredient mayalso be depicted as X: Y; wherein X is the parts by weight of FormulaOne and Y is the parts by weight of the active ingredient. The numericalrange of the parts by weight for X is 0<X≤100 and the parts by weightfor Y is 0<Y≤100 and is shown graphically in Table 4. By way ofnon-limiting example, the weight ratio of Formula One to an activeingredient may be 20:1.

TABLE 4 active 100 X, Y X, Y X, Y ingredient 50 X, Y X, Y X, Y X, Y X, Y(Y) Parts 20 X, Y X, Y X, Y X, Y X, Y by weight 15 X, Y X, Y X, Y X, YX, Y 10 X, Y X, Y 5 X, Y X, Y X, Y X, Y 3 X, Y X, Y X, Y X, Y X, Y X, YX, Y 2 X, Y X, Y X, Y X, Y X, Y 1 X, Y X, Y X, Y X, Y X, Y X, Y X, Y X,Y X, Y 1 2 3 5 10 15 20 50 100 Formula One, also known as F1, (X) Partsby weight

Ranges of weight ratios of Formula One to an active ingredient may bedepicted as X₁:Y₁ to X₂:Y₂, wherein X and Y are defined as above.

In one embodiment, the range of weight ratios may be X₁:Y₁ to X₂:Y₂,wherein X₁>Y₁ and X₂<Y₂. By way of non-limiting example, the range of aweight ratio of Formula One to an active ingredient may be between 3:1and 1:3, inclusive of the endpoints.

In another embodiment, the range of weight ratios may be X₁:Y₁ to X₂:Y₂,wherein X₁>Y₁ and X₂>Y₂. By way of non-limiting example, the range ofweight ratio of Formula One to an active ingredient may be between 15:1and 3:1, inclusive of the endpoints.

In another embodiment, the range of weight ratios may be X₁:Y₁ to X₂:Y₂,wherein X₁<Y₁ and X₂<Y₂. By way of non-limiting example, the range ofweight ratios of Formula One to an active ingredient may be betweenabout 1:3 and about 1:20, inclusive of the endpoints.

Formulations

A pesticide is often not suitable for application in its pure form. Itis usually necessary to add other substances so that the pesticide maybe used at the required concentration and in an appropriate form,permitting ease of application, handling, transportation, storage, andmaximum pesticidal activity. Thus, pesticides are formulated into, forexample, baits, concentrated emulsions, dusts, emulsifiableconcentrates, fumigants, gels, granules, microencapsulations, seedtreatments, suspension concentrates, suspoemulsions, tablets, watersoluble liquids, water dispersible granules or dry flowables, wettablepowders, and ultra-low volume solutions.

Pesticides are applied most often as aqueous suspensions or emulsionsprepared from concentrated formulations of such pesticides. Suchwater-soluble, water-suspendable, or emulsifiable formulations may besolids usually known as wettable powders, water dispersible granules,liquids usually known as emulsifiable concentrates, or aqueoussuspensions. Wettable powders, which may be compacted to form waterdispersible granules, comprise an intimate mixture of the pesticide, acarrier, and surfactants. The concentration of the pesticide is usuallyfrom about 10% to about 90% by weight. The carrier is usually selectedfrom among the attapulgite clays, the montmorillonite clays, thediatomaceous earths, or the purified silicates. Effective surfactants,comprising from about 0.5% to about 10% of the wettable powder, arefound among sulfonated lignins, condensed naphthalenesulfonates,naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates, andnon-ionic surfactants such as ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of pesticides comprise a convenientconcentration of a pesticide, such as from about 50 to about 500 gramsper liter of liquid dissolved in a carrier that is either a watermiscible solvent or a mixture of water-immiscible organic solvent andemulsifiers. Useful organic solvents include aromatics, especiallyxylenes and petroleum fractions, especially the high-boilingnaphthalenic and olefinic portions of petroleum such as heavy aromaticnaphtha. Other organic solvents may also be used, such as the terpenicsolvents including rosin derivatives, aliphatic ketones such ascyclohexanone, and complex alcohols such as 2-ethoxyethanol. Suitableemulsifiers for emulsifiable concentrates are selected from conventionalanionic and non-ionic surfactants.

Aqueous suspensions comprise suspensions of water-insoluble pesticidesdispersed in an aqueous carrier at a concentration in the range fromabout 5% to about 50% by weight. Suspensions are prepared by finelygrinding the pesticide and vigorously mixing it into a carrier comprisedof water and surfactants. Ingredients, such as inorganic salts andsynthetic or natural gums may, also be added to increase the density andviscosity of the aqueous carrier. It is often most effective to grindand mix the pesticide at the same time by preparing the aqueous mixtureand homogenizing it in an implement such as a sand mill, ball mill, orpiston-type homogenizer. The pesticide in suspension might bemicroencapsulated in plastic polymer.

Oil dispersions (OD) comprise suspensions of organic solvent-insolublepesticides finely dispersed in a mixture of organic solvent andemulsifiers at a concentration in the range from about 2% to about 50%by weight. One or more pesticides might be dissolved in the organicsolvent. Useful organic solvents include aromatics, especially xylenesand petroleum fractions, especially the high-boiling naphthalenic andolefinic portions of petroleum such as heavy aromatic naphtha. Othersolvents may include vegetable oils, seed oils, and esters of vegetableand seed oils. Suitable emulsifiers for oil dispersions are selectedfrom conventional anionic and non-ionic surfactants. Thickeners orgelling agents are added in the formulation of oil dispersions to modifythe rheology or flow properties of the liquid and to prevent separationand settling of the dispersed particles or droplets.

Pesticides may also be applied as granular compositions that areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the pesticide,dispersed in a carrier that comprises clay or a similar substance. Suchcompositions are usually prepared by dissolving the pesticide in asuitable solvent and applying it to a granular carrier, which has beenpre-formed to the appropriate particle size, in the range of from about0.5 mm to about 3 mm. Such compositions may also be formulated by makinga dough or paste of the carrier and molecule, and then crushing anddrying to obtain the desired granular particle size. Another form ofgranules is a water emulsifiable granule (EG). It is a formulationconsisting of granules to be applied as a conventional oil-in-wateremulsion of the active ingredient(s), either solubilized or diluted inan organic solvent, after disintegration and dissolution in water. Wateremulsifiable granules comprise one or several active ingredient(s),either solubilized or diluted in a suitable organic solvent that is(are) absorbed in a water soluble polymeric shell or some other type ofsoluble or insoluble matrix.

Dusts containing a pesticide are prepared by intimately mixing thepesticide in powdered form with a suitable dusty agricultural carrier,such as kaolin clay, ground volcanic rock, and the like. Dusts cansuitably contain from about 1% to about 10% of the pesticide. Dusts maybe applied as a seed dressing or as a foliage application with a dustblower machine.

It is equally practical to apply a pesticide in the form of a solutionin an appropriate organic solvent, usually petroleum oil, such as thespray oils, which are widely used in agricultural chemistry.

Pesticides can also be applied in the form of an aerosol composition. Insuch compositions, the pesticide is dissolved or dispersed in a carrier,which is a pressure-generating propellant mixture. The aerosolcomposition is packaged in a container from which the mixture isdispensed through an atomizing valve.

Pesticide baits are formed when the pesticide is mixed with food or anattractant or both. When the pests eat the bait, they also consume thepesticide. Baits may take the form of granules, gels, flowable powders,liquids, or solids. Baits may be used in pest harborages.

Fumigants are pesticides that have a relatively high vapor pressure andhence can exist as a gas in sufficient concentrations to kill pests insoil or enclosed spaces. The toxicity of the fumigant is proportional toits concentration and the exposure time. They are characterized by agood capacity for diffusion and act by penetrating the pest'srespiratory system or being absorbed through the pest's cuticle.Fumigants are applied to control stored product pests under gas proofsheets, in gas sealed rooms or buildings, or in special chambers.

Pesticides may be microencapsulated by suspending the pesticideparticles or droplets in polymers of various types. By altering thechemistry of the polymer or by changing factors in the processing,microcapsules may be formed of various sizes, solubility, wallthicknesses, and degrees of penetrability. These factors govern thespeed with which the active ingredient within is released, which inturn, affects the residual performance, speed of action, and odor of theproduct. The microcapsules might be formulated as suspensionconcentrates or water dispersible granules.

Oil solution concentrates are made by dissolving pesticide in a solventthat will hold the pesticide in solution. Oil solutions of a pesticideusually provide faster knockdown and kill of pests than otherformulations due to the solvents themselves having pesticidal action andthe dissolution of the waxy covering of the integument increasing thespeed of uptake of the pesticide. Other advantages of oil solutionsinclude better storage stability, better penetration of crevices, andbetter adhesion to greasy surfaces.

Another embodiment is an oil-in-water emulsion, wherein the emulsioncomprises oily globules which are each provided with a lamellar liquidcrystal coating and are dispersed in an aqueous phase, wherein each oilyglobule comprises at least one molecule which is agriculturally active,and is individually coated with a monolamellar or oligolamellar layercomprising: (1) at least one non-ionic lipophilic surface-active agent,(2) at least one non-ionic hydrophilic surface-active agent, and (3) atleast one ionic surface-active agent, wherein the globules having a meanparticle diameter of less than 800 nanometers.

Other Formulation Components

Generally, when Formula One is used in a formulation, such formulationcan also contain other components. These components include, but are notlimited to (this is a non-exhaustive and non-mutually exclusive list),wetters, spreaders, stickers, penetrants, buffers, sequestering agents,drift reduction agents, compatibility agents, anti-foam agents, cleaningagents, and emulsifiers. A few components are described forthwith.

A wetting agent is a substance that when added to a liquid increases thespreading or penetration power of the liquid by reducing the interfacialtension between the liquid and the surface on which it is spreading.Wetting agents are used for two main functions in agrochemicalformulations: during processing and manufacture to increase the rate ofwetting of powders in water to make concentrates for soluble liquids orsuspension concentrates; and during mixing of a product with water in aspray tank to reduce the wetting time of wettable powders and to improvethe penetration of water into water-dispersible granules. Examples ofwetting agents used in wettable powder, suspension concentrate, andwater-dispersible granule formulations are: sodium lauryl sulfate,sodium dioctyl sulfosuccinate, alkyl phenol ethoxylates, and aliphaticalcohol ethoxylates.

A dispersing agent is a substance that adsorbs onto the surface ofparticles, helps to preserve the state of dispersion of the particles,and prevents them from reaggregating. Dispersing agents are added toagrochemical formulations to facilitate dispersion and suspension duringmanufacture, and to ensure the particles redisperse into water in aspray tank. They are widely used in wettable powders, suspensionconcentrates, and water-dispersible granules. Surfactants that are usedas dispersing agents have the ability to adsorb strongly onto a particlesurface and provide a charged or steric barrier to reaggregation ofparticles. The most commonly used surfactants are anionic, non-ionic, ormixtures of the two types. For wettable powder formulations, the mostcommon dispersing agents are sodium lignosulfonates. For suspensionconcentrates, very good adsorption and stabilization are obtained usingpolyelectrolytes, such assodium-naphthalene-sulfonate-formaldehyde-condensates. Tristyrylphenolethoxylate phosphate esters are also used. Non-ionics such asalkylarylethylene oxide condensates and EO—PO block copolymers aresometimes combined with anionics as dispersing agents for suspensionconcentrates. In recent years, new types of very high molecular weightpolymeric surfactants have been developed as dispersing agents. Thesehave very long hydrophobic ‘backbones’ and a large number of ethyleneoxide chains forming the ‘teeth’ of a ‘comb’ surfactant. These highmolecular weight polymers can give very good long-term stability tosuspension concentrates because the hydrophobic backbones have manyanchoring points onto the particle surfaces. Examples of dispersingagents used in agrochemical formulations are: sodium lignosulfonates,sodium naphthalene sulfonate formaldehyde condensates,tristyrylphenol-ethoxylate-phosphate-esters, aliphatic alcoholethoxylates, alkyl ethoxylates, EO—PO block copolymers, and graftcopolymers.

An emulsifying agent is a substance that stabilizes a suspension ofdroplets of one liquid phase in another liquid phase. Without theemulsifying agent, the two liquids would separate into two immiscibleliquid phases. The most commonly used emulsifier blends contain analkylphenol or an aliphatic alcohol with twelve or more ethylene oxideunits and the oil-soluble calcium salt of dodecylbenzenesulfonic acid. Arange of hydrophile-lipophile balance (“HLB”) values from about 8 toabout 18 will normally provide good stable emulsions. Emulsion stabilitycan sometimes be improved by the addition of a small amount of an EO—POblock copolymer surfactant.

A solubilizing agent is a surfactant that will form micelles in water atconcentrations above the critical micelle concentration. The micellesare then able to dissolve or solubilize water-insoluble materials insidethe hydrophobic part of the micelle. The types of surfactants usuallyused for solubilization are non-ionics, sorbitan monooleates, sorbitanmonooleate ethoxylates, and methyl oleate esters.

Surfactants are sometimes used, either alone or with other additivessuch as mineral or vegetable oils as adjuvants to spray-tank mixes toimprove the biological performance of the pesticide on the target. Thetypes of surfactants used for bioenhancement depend generally on thenature and mode of action of the pesticide. However, they are oftennon-ionics such as: alkyl ethoxylates, linear aliphatic alcoholethoxylates, and aliphatic amine ethoxylates.

A carrier or diluent in an agricultural formulation is a material addedto the pesticide to give a product of the required strength. Carriersare usually materials with high absorptive capacities, while diluentsare usually materials with low absorptive capacities. Carriers anddiluents are used in the formulation of dusts, wettable powders,granules, and water-dispersible granules.

Organic solvents are used mainly in the formulation of emulsifiableconcentrates, oil-in-water emulsions, suspoemulsions, oil dispersions,and ultra-low volume formulations, and to a lesser extent, granularformulations. Sometimes mixtures of solvents are used. The first maingroups of solvents are aliphatic paraffinic oils such as kerosene orrefined paraffins. The second main group (and the most common) comprisesthe aromatic solvents such as xylene and higher molecular weightfractions of C9 and C10 aromatic solvents. Chlorinated hydrocarbons areuseful as cosolvents to prevent crystallization of pesticides when theformulation is emulsified into water. Alcohols are sometimes used ascosolvents to increase solvent power. Other solvents may includevegetable oils, seed oils, and esters of vegetable and seed oils.

Thickeners or gelling agents are used mainly in the formulation ofsuspension concentrates, oil dispersions, emulsions and suspoemulsionsto modify the rheology or flow properties of the liquid and to preventseparation and settling of the dispersed particles or droplets.Thickening, gelling, and anti-settling agents generally fall into twocategories, namely water-insoluble particulates and water-solublepolymers. It is possible to produce suspension concentrate and oildispersion formulations using clays and silicas. Examples of these typesof materials, include, but are not limited to, montmorillonite,bentonite, magnesium aluminum silicate, and attapulgite. Water-solublepolysaccharides in water based suspension concentrates have been used asthickening-gelling agents for many years. The types of polysaccharidesmost commonly used are natural extracts of seeds and seaweeds or aresynthetic derivatives of cellulose. Examples of these types of materialsinclude, but are not limited to, guar gum, locust bean gum, carrageenan,alginates, methyl cellulose, sodium carboxymethyl cellulose (SCMC), andhydroxyethyl cellulose (HEC). Other types of anti-settling agents arebased on modified starches, polyacrylates, polyvinyl alcohol, andpolyethylene oxide. Another good anti-settling agent is xanthan gum.

Microorganisms can cause spoilage of formulated products. Therefore,preservation agents are used to eliminate or reduce their effect.Examples of such agents include, but are not limited to: propionic acidand its sodium salt, sorbic acid and its sodium or potassium salts,benzoic acid and its sodium salt, p-hydroxybenzoic acid sodium salt,methyl p-hydroxybenzoate, and 1,2-benzisothiazolin-3-one (BIT).

The presence of surfactants often causes water-based formulations tofoam during mixing operations in production and in application through aspray tank. In order to reduce the tendency to foam, anti-foam agentsare often added either during the production stage or before fillinginto bottles. Generally, there are two types of anti-foam agents, namelysilicones and non-silicones. Silicones are usually aqueous emulsions ofdimethyl polysiloxane, while the non-silicone anti-foam agents arewater-insoluble oils, such as octanol and nonanol, or silica. In bothcases, the function of the anti-foam agent is to displace the surfactantfrom the air-water interface.

“Green” agents (e.g., adjuvants, surfactants, solvents) can reduce theoverall environmental footprint of crop protection formulations. Greenagents are biodegradable and generally derived from natural and/orsustainable sources, e.g. plant and animal sources. Specific examplesare: vegetable oils, seed oils, and esters thereof, also alkoxylatedalkyl polyglucosides.

Applications

Formula One may be applied to any locus. Particular loci to apply suchmolecules include loci where alfalfa, almonds, apples, barley, beans,canola, corn, cotton, crucifers, flowers, fodder species (Rye Grass,Sudan Grass, Tall Fescue, Kentucky Blue Grass, and Clover), fruits,lettuce, oats, oil seed crops, oranges, peanuts, pears, peppers,potatoes, rice, sorghum, soybeans, strawberries, sugarcane, sugarbeets,sunflowers, tobacco, tomatoes, wheat (for example, Hard Red WinterWheat, Soft Red Winter Wheat, White Winter Wheat, Hard Red Spring Wheat,and Durum Spring Wheat), and other valuable crops are growing or theseeds thereof are going to be planted.

Formula One may also be applied where plants, such as crops, are growingand where there are low levels (even no actual presence) of pests thatcan commercially damage such plants. Applying such molecules in suchlocus is to benefit the plants being grown in such locus. Such benefits,may include, but are not limited to: helping the plant grow a betterroot system; helping the plant better withstand stressful growingconditions; improving the health of a plant; improving the yield of aplant (e.g. increased biomass and/or increased content of valuableingredients); improving the vigor of a plant (e.g. improved plant growthand/or greener leaves); improving the quality of a plant (e.g. improvedcontent or composition of certain ingredients); and improving thetolerance to abiotic and/or biotic stress of the plant.

Formula One may be applied with ammonium sulfate when growing variousplants as this may provide additional benefits.

Formula One may be applied on, in, or around plants genetically modifiedto express specialized traits, such as Bacillus thuringiensis (forexample, Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A,Cry3Ab, Cry3Bb, Cry34Ab1/Cry35Ab1), other insecticidal toxins, or thoseexpressing herbicide tolerance, or those with “stacked” foreign genesexpressing insecticidal toxins, herbicide tolerance,nutrition-enhancement, or any other beneficial traits.

Formula One may be applied to the foliar and/or fruiting portions ofplants to control pests. Either such molecules will come in directcontact with the pest, or the pest will consume such molecules wheneating the plant or while extracting sap or other nutrients from theplant.

Formula One may also be applied to the soil, and when applied in thismanner, root and stem feeding pests may be controlled. The roots mayabsorb such molecules thereby taking it up into the foliar portions ofthe plant to control above ground chewing and sap feeding pests.

Systemic movement of pesticides in plants may be utilized to controlpests on one portion of the plant by applying (for example by spraying alocus) a molecule of Formula One to a different portion of the plant.For example, control of foliar-feeding insects may be achieved by dripirrigation or furrow application, by treating the soil with for examplepre- or post-planting soil drench, or by treating the seeds of a plantbefore planting.

Formula One may be used with baits. Generally, with baits, the baits areplaced in the ground where, for example, termites can come into contactwith, and/or be attracted to, the bait. Baits can also be applied to asurface of a building, (horizontal, vertical, or slant surface) where,for example, ants, termites, cockroaches, and flies, can come intocontact with, and/or be attracted to, the bait.

Formula One may be encapsulated inside, or placed on the surface of acapsule. The size of the capsules can range from nanometer size (about100-900 nanometers in diameter) to micrometer size (about 10-900 micronsin diameter).

Formula One may be applied to eggs of pests. Because of the uniqueability of the eggs of some pests to resist certain pesticides, repeatedapplications of such molecules may be desirable to control newly emergedlarvae.

Formula One may be applied as seed treatments. Seed treatments may beapplied to all types of seeds, including those from which plantsgenetically modified to express specialized traits will germinate.Representative examples include those expressing proteins toxic toinvertebrate pests, such as Bacillus thuringiensis or other insecticidaltoxins, those expressing herbicide tolerance, such as “Roundup Ready”seed, or those with “stacked” foreign genes expressing insecticidaltoxins, herbicide tolerance, nutrition-enhancement, drought tolerance,or any other beneficial traits. Furthermore, such seed treatments withFormula One may further enhance the ability of a plant to withstandstressful growing conditions better. This results in a healthier, morevigorous plant, which can lead to higher yields at harvest time.Generally, about 0.0025 mg of Formula One per seed to about 2.0 mg ofFormula One per seed is useful, amounts of about 0.01 mg of Formula Oneper seed to about 1.75 mg of Formula One per seed is useful, amounts of0.1 mg of Formula One per seed to about 1.5 mg of Formula One per seedis useful, amounts of 0.25 mg of Formula One per seed to about 0.75 mgof Formula One per seed is useful. In general, an amount of about 0.5 mgof Formula One per seed in useful.

Formula One may be applied with one or more active ingredients in a soilamendment.

Formula One may be used for controlling endoparasites and ectoparasitesin the veterinary medicine sector or in the field of non-human-animalkeeping. Such molecules may be applied by oral administration in theform of, for example, tablets, capsules, drinks, granules, by dermalapplication in the form of, for example, dipping, spraying, pouring on,spotting on, and dusting, and by parenteral administration in the formof, for example, an injection.

Formula One may also be employed advantageously in livestock keeping,for example, cattle, chickens, geese, goats, pigs, sheep, and turkeys.They may also be employed advantageously in pets such as, horses, dogs,and cats. Particular pests to control would be flies, fleas, and ticksthat are bothersome to such animals. Suitable formulations areadministered orally to the animals with the drinking water or feed. Thedosages and formulations that are suitable depend on the species.

Formula One may also be used for controlling parasitic worms, especiallyof the intestine, in the animals listed above.

Formula One may also be employed in therapeutic methods for human healthcare. Such methods include, but are limited to, oral administration inthe form of, for example, tablets, capsules, drinks, granules, and bydermal application.

Formula One may also be applied to invasive pests. Pests around theworld have been migrating to new environments (for such pest) andthereafter becoming a new invasive species in such new environment. Suchmolecules may also be used on such new invasive species to control themin such new environments.

Plant viruses cause an estimated US$60 billion loss in crop yieldsworldwide each year. Many plant viruses need to be transmitted by avector, most often insects, examples of which are leafhoppers and planthoppers. However, nematodes also have been shown to transmit viruses.Nematodes transmit plant viruses by feeding on roots. Formula One mayalso be applied to a plant in order to inhibit pests that carry plantvirus so that this reduces the chance that such plant viruses aretransmitted from the pest to the plant.

Consequently, in light of the above the following additional,non-exhaustive, details (D) are provided.

-   -   1D. A molecule having the following formula

Formula One Also Known as F1

and N-oxides, agriculturally acceptable acid addition salts, saltderivatives, solvates, ester derivatives, polymorphs, isotopes, resolvedstereoisomers, and tautomers, thereof.

-   -   2D. A composition comprising a molecule according to 1D and        further comprising a carrier.    -   3D. A composition according to 2D said composition further        comprising an active ingredient.    -   4D. A composition according to any of the previous details, said        composition further comprising an active ingredient selected        from acaricides, algicides, antifeedants, avicides,        bactericides, bird repellents, chemosterilants, fungicides,        herbicide safeners, herbicides, insect attractants, insect        repellents, insecticides, mammal repellents, mating disrupters,        molluscicides, nematicides, plant activators, plant health        stimulators or promoters, nitrification inhibitors, plant growth        regulators, rodenticides, synergists, and virucides.    -   5D. A composition according to any of the previous details, said        composition further comprising an active ingredient selected        from AIGA.    -   6D. A composition according to any of the previous details, said        composition further comprising an active ingredient selected        from AI-1.    -   7D. A composition according to any of the previous details, said        composition further comprising an active ingredient selected        from AI-2.    -   8D. A composition according to any of the previous details, said        composition further comprising Lotilaner.    -   9D. A composition according to any of the previous details, said        composition further comprising a molecule selected from Table A.    -   10D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from AIGA-2.    -   11D. A composition according to any of the previous details,        said composition further comprising a biopesticide.    -   12D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Acetylcholinesterase (AChE) inhibitors.    -   13D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from GABA-gated chloride channel antagonists.    -   14D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Sodium channel modulators.    -   15D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Nicotinic acetylcholine receptor (nAChR) agonists.    -   16D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Nicotinic acetylcholine receptor (nAChR)        allosteric activators.    -   17D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Chloride channel activators.    -   18D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Juvenile hormone mimics.    -   19D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Miscellaneous nonspecific (multi-site) inhibitors.    -   20D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Modulators of Chordotonal Organs.    -   21D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Mite growth inhibitors.    -   22D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Microbial disruptors of insect midgut membranes.    -   23D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Inhibitors of mitochondrial ATP synthase.    -   24D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Uncouplers of oxidative phosphorylation via        disruption of the proton gradient.    -   25D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Nicotinic acetylcholine receptor (nAChR) channel        blockers.    -   26D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Inhibitors of chitin biosynthesis, type 0.    -   27D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Inhibitors of chitin biosynthesis, type 1.    -   28D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Moulting disruptor, Dipteran.    -   29D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Ecdysone receptor agonists.    -   30D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Octopamine receptor agonists.    -   31D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Mitochondrial complex III electron transport        inhibitors.    -   32D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Mitochondrial complex I electron transport        inhibitors.    -   33D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Voltage-dependent sodium channel blockers.    -   34D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Inhibitors of acetyl CoA carboxylase.    -   35D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Mitochondrial complex IV electron transport        inhibitors.    -   36D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Mitochondrial complex II electron transport        inhibitors.    -   37D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Ryanodine receptor modulators.    -   38D. A composition according to any of the previous details,        said composition further comprising an active ingredient        selected from Group UN.    -   39D. A composition according to any of the previous details,        said composition further comprising chlorantraniliprole.    -   40D. A composition according to any of the previous details,        said composition further comprising chlorpyrifos.    -   41D. A composition according to any of the previous details,        said composition further comprising cyantraniliprole.    -   42D. A composition according to any of the previous details,        said composition further comprising methomyl.    -   43D. A composition according to any of the previous details,        said composition further comprising methoxyfenozide.    -   44D. A composition according to any of the previous details,        said composition further comprising oxamyl.    -   45D. A composition according to any of the previous details,        said composition further comprising spinetoram.    -   46D. A composition according to any of the previous details,        said composition further comprising spinosad.    -   47D. A composition according to any of the previous details,        said composition further comprising sulfoxaflor.    -   48D. A composition according to any of the previous details,        said composition further comprising triflumezopyrim.    -   49D. A composition according to any of the previous details,        said composition further comprising beta-cyfluthrin.    -   50D. A composition according to any of the previous details,        said composition further comprising clothianidin.    -   51D. A composition according to any of the previous details,        said composition further comprising cyfluthrin.    -   52D. A composition according to any of the previous details,        said composition further comprising flubendiamide.    -   53D. A composition according to any of the previous details,        said composition further comprising fluopyram.    -   54D. A composition according to any of the previous details,        said composition further comprising flupyradifurone.    -   55D. A composition according to any of the previous details,        said composition further comprising imidacloprid.    -   56D. A composition according to any of the previous details,        said composition further comprising spiromesifen.    -   57D. A composition according to any of the previous details,        said composition further comprising spirotetramat.    -   58D. A composition according to any of the previous details,        said composition further comprising spirodiclofen.    -   59D. A composition according to any of the previous details,        said composition further comprising tetraniliprole.    -   60D. A composition according to any of the previous details,        said composition further comprising thiodicarb.    -   61D. A composition according to any of the previous details,        said composition further comprising thiacloprid.    -   62D. A composition according to any of the previous details,        said composition further comprising alpha-cypermethrin.    -   63D. A composition according to any of the previous details,        said composition further comprising cyflumetofen.    -   64D. A composition according to any of the previous details,        said composition further comprising fipronil.    -   65D. A composition according to any of the previous details,        said composition further comprising metaflumizone.    -   66D. A composition according to any of the previous details,        said composition further comprising zeta-cypermethrin.    -   67D. A composition according to any of the previous details,        said composition further comprising afidopyropen.    -   68D. A composition according to any of the previous details        wherein the weight ratio of F1 to an active ingredient is 100:1        to 1:100.    -   69D. A composition according to any of the previous details        wherein the weight ratio of F1 to an active ingredient is 50:1        to 1:50.    -   70D. A composition according to any of the previous details        wherein the weight ratio of F1 to an active ingredient is 20:1        to 1:20.    -   71D. A composition according to any of the previous details        wherein the weight ratio of F1 to an active ingredient is 10:1        to 1:10.    -   72D. A composition according to any of the previous details        wherein the weight ratio of F1 to an active ingredient is 5:1 to        1:5.    -   73D. A composition according to any of the previous details        wherein the weight ratio of F1 to an active ingredient is 3:1 to        1:3.    -   74D. A composition according to any of the previous details        wherein the weight ratio of F1 to an active ingredient is 2:1 to        1:2.    -   75D. A composition according to any of the previous details        wherein the weight ratio of F1 to an active ingredient is 1:1.    -   76D. A composition according to any of the details wherein the        weight ratio of F1 to an active ingredient is X:Y; wherein X is        the parts by weight of F1 and Y is the parts by weight of an        active ingredient; further wherein the numerical range of the        parts by weight for X is 0<X≤100 and the parts by weight for Y        is 0<Y≤100; and further wherein X and Y are selected from Table        4.    -   77D. A process to control a pest said process comprising        applying to a locus a pesticidally effective amount of        composition comprising F1.    -   78D. A process to control a pest said process comprising        applying to a locus a pesticidally effective amount of a        composition according to any one of the previous details 2D        through 76D.    -   79D. A process according to details 77D or 78D wherein said pest        is selected from the group consisting of the group consisting of        ants, aphids, bed bugs, beetles, bristletails, caterpillars,        cockroaches, crickets, earwigs, fleas, flies, grasshoppers,        grubs, leafhoppers, lice, locusts, maggots, mealybugs, mites,        nematodes, planthoppers, psyllids, sawflies, scales, silverfish,        slugs, snails, spiders, springtails, stink bugs, symphylans,        termites, thrips, ticks, wasps, whiteflies, and wireworms.    -   80D. A process according to details 77D or 78D wherein said pest        is a sap-feeding pest.    -   81D. A process according to details 77D or 78D wherein said pest        is an aphid.    -   82D. A process according to details 77D or 78D wherein said pest        is a planthopper.    -   83D. A process according to details 77D or 78D wherein said pest        is from the Order Anoplura or Hemiptera.    -   84D. A process according to details 77D or 78D wherein said        composition is applied to the soil.    -   85D. A process according to details 77D or 78D wherein said        composition is applied to the foliar portions of a plant.    -   86D. A process according to details 77D or 78D wherein said        locus rice, corn, soybean, cotton, potato, sorghum, sugarcane,        canola, tea, grape, wheat, barley, alfalfa, or other fruits or        vegetables are growing.    -   87D. A composition according to any of the previous details 2D        through 76D, said composition further comprising a seed.    -   88D. A composition according to detail 87D, wherein said seed is        a cotton seed, sunflower seed, rice seed, sugarbeet seed,        oilseed rape seed, corn seed, wheat seed, barley seed, millet        seed, sorghum seed, buckwheat seed, oat seed, rye seed, soybean        seed, or quinoa seed.    -   89D. A composition according to detail 87D wherein about 0.0025        mg of Formula One per seed to about 2.0 mg of Formula One per        seed is used.

The headings in this document are for convenience only and must not beused to interpret any portion hereof.

We claim:
 1. A composition comprising (a) a molecule of Formula One (F1)

and (b) an active ingredient selected from the group consisting of1,3-dichloropropene, chlorantraniliprole, chlorpyrifos,cyantraniliprole, hexaflumuron, methomyl, methoxyfenozide, noviflumuron,oxamyl, spinetoram, spinosad, sulfoxaflor, triflumezopyrim, acequinocyl,acetamiprid, acetoprole, avermectin, azinphos-methyl, bifenazate,bifenthrin, carbaryl, carbofuran, chlorfenapyr, chlorfluazuron,chromafenozide, clothianidin, cyfluthrin, cypermethrin, deltamethrin,diafenthiuron, emamectin benzoate, endosulfan, esfenvalerate, ethiprole,etoxazole, fipronil, flonicamid, fluacrypyrim, gamma-cyhalothrin,halofenozide, indoxacarb, lambda-cyhalothrin, lufenuron, malathion,novaluron, permethrin, pyridalyl, pyrimidifen, spirodiclofen,tebufenozide, thiacloprid, thiamethoxam, thiodicarb, tolfenpyrad, andzeta-cypermethrin.
 2. A composition according to claim 1, wherein saidactive ingredient is chlorantraniliprole.
 3. A composition according toclaim 1, wherein said active ingredient is cyantraniliprole.
 4. Acomposition according to claim 1, wherein said active ingredient ismethomyl.
 5. A composition according to claim 1, wherein said activeingredient is methoxyfenozide.
 6. A composition according to claim 1,wherein said active ingredient is spinetoram.
 7. A composition accordingto claim 1, wherein said active ingredient is spinosad.
 8. A compositionaccording to claim 1, wherein said active ingredient is sulfoxaflor. 9.A composition according to claim 1, wherein said active ingredient istriflumezopyrim.
 10. A composition according to claim 1, wherein saidactive ingredient is acetamiprid.
 11. A composition according to claim1, wherein said active ingredient is bifenthrin.
 12. A compositionaccording to claim 1, wherein said active ingredient is clothianidin.13. A composition according to claim 1, wherein said active ingredientis ethiprole.
 14. A composition according to claim 1, wherein saidactive ingredient is fipronil.
 15. A composition according to claim 1,wherein said active ingredient is flonicamid.
 16. A compositionaccording to claim 1, wherein said active ingredient is indoxacarb. 17.A composition according to claim 1, wherein said active ingredient islambda-cyhalothrin.
 18. A composition according to claim 1, wherein saidactive ingredient is thiacloprid.
 19. A composition according to claim1, wherein said active ingredient is thiamethoxam.
 20. A compositionaccording to claim 1, wherein the weight ratio of F1 to said activeingredient is 100:1 to 1:100.